Okay, good morning everybody. It's a pleasure to be in the Homeova Center. I've been here many times, but particularly nice to see Professor Arvind Kumar, Professor Pradhan, the previous directors and of course the present director has an obligation to be here on this day and they are the free will. And then my colleagues in chemistry, one thing nice about place like this is that every year you get a set of bright new faces and by the time you come back from those of you who get selected, go to the International Chemistry Olympiad and come and receive your medals or you have received your medals elsewhere and get some recognition, some prize in this country, as much as you don't like, you become history. Because now the moment you come back, I've seen Professor Arvind Kumar and company working hard. This year the medalists have come back. They've already started. I had the privilege of working with Dr. Arvind Kumar years ago. I probably should say some of this in the evening, in the later function rather than this technical thought. But let me say this, if I say a few couple of more words later on, doesn't matter. They're already working for the next year. That's the way it goes. Now in this process, some of us are asked to come and talk to you about certain things in chemistry. That's what I'm going to do. And this time I got my talk wetted by my daughter who wanted to make sure that it is at the level of class 11 and 12, she knows that you are going for this and you come back and then you will do whatever you want to, science, technology, medicine, whatever. So I hope I make sense, 11 o'clock to 11, right? In the next 50 minutes, I hope whatever I say makes sense. But the main point I want to drive home here is that every time we teach something, a few years later, things change. Much before Ankush came as a PhD student, sorry, as a master student in IIT Kanpur, I taught several batches. Some of the things that I used to make statements when I started as a faculty member are no longer true. And what I want to show here is how science keeps on moving, progressing and the frontiers of science get shifted, keeps moving. And here, this is not the place to talk about science and technology. This is possible when technological development takes place. Technological development takes place because of scientific development. So they both go hand in hand. So here, what is it that we are trying to say to look at? How to measure reaction rates? You know, the mother or Dadima makes curd and says beta after three, four hours, put it in the fridge. There is some technical problem. But you can see the curd is set. And of course, difficult to measure in real time how the curd is getting set. If you keep opening it and so on, you will disturb it. But at the end of a few hours, you know the curd is set. Inversion of sucrose and those are, you must be, all of you, anybody who does not know about inversion of sucrose, everybody knows, right? So the sugar, which is called dextrose as a positive optical activity, put from water and acid, it hydrolyzes and gives glucose and fructose and the optical activity changes to negative. So this is the sign changes inversion. Historically, it was a very important reaction for which the rates were measured, not only at room temperature but a few degrees above and a few degrees below. And based on that data analysis, analysis of that later led to Arrhenius equation. But this is a reaction that you can observe in a few minutes. Actually, a watch is good enough. But there are reactions which take place in a second, in a few seconds. So today, we don't need a stopwatch. We used to use a stopwatch, but you can use your smartphone and measure it. But anything less than that is going to be difficult for you to measure with the normal gadgets that you have. You need to go to milli seconds. That was a technological challenge by the 60s. So people had to come up with indirect means. They couldn't come up with a clock that will show milli seconds, but they had to do something that they could observe in milli seconds. And then there were other people who don't wait for things to happen. They are the one leaders of science. They made it possible to measure things in microseconds. Then with the lasers, 10 to the power of minus 9, 10 to the power of minus 12, 10 to the power of minus 15 became possible. We will talk a little bit about these things. Today, the challenging task is to work with atoseconds. We are not going to say how we produce atosecond pulse. That is not a chemist's job in some sense. But what can we make use of, how we can use the atosecond and learn something about chemistry? Ultimately, if I am a chemist, I need to know what I can do for chemistry. At every stage, there has been technological developments. And you will see as to where these developments are needed. And when you do something outstanding, people do appreciate it. And one of the appreciation that people are happy, I don't want to say look forward to, some people look forward to. And it gets done. So, in 1967, these three gentlemen got Nobel Prize for being able to measure reaction rate in millisecond in methods called a T-jump, where you suddenly spike the temperature and watch the system relax and make measurements and inferences. This was a case where you have a flash photolysis. You have two plates and you build charge and let a flash come like a lightning and use that to record events in the microsecond scale. Fast forward about 30 years later, Ahmaj Jwail, he made measurements using femtosecond pumps. So, when he did this, people used to criticize, well, he didn't develop femtosecond lasers. It was Shank who developed, he didn't develop this technique. What is called the pump and probe? I'll tell you what it means. But he put together those things and he did something more than that. That is what makes today's talk worthwhile. So, when you want to look at things, you need to, if you want to look at space, in space and time, you need things to measure. When I grew up, we used to have a foot scale with inches and then somewhere along the line, a teacher told us, now you must use the decimal units. We switched over to a meter scale. So, I know how to measure in centimeter and I look for one-tenth of it millimeter. And then we went to college. We were very happy to see this quantity called the micrometer gauge. Then with screw gauge is what it used to call. We had a lot of difficulties in measuring. We didn't know what we were doing, but we did some experiments. We made some measurements and got some marks and so on. But now I know that we were doing measurements in micron scale. But today everybody wants to talk about nano. Somebody will tell you, your neighbor will come and tell you, beta was sub-olympiad. You work in nano. Uncle, we don't know what nano is. You work in nano. So, everybody wants to do nanometer scale. We used to call them as collides. Micron or sub-micron things and we used to say how to be used to talk about tindall effect. Nowadays you don't get to see in such air conditioned rooms the tindall effect, the classes that we used to study. You will have some sunlight coming in. There was enough dust in the air. Teacher would simply say, beta, you look at this. This is what is called the tindall effect. But today you do things in very careful conditions, measure and say this is of the order of several nanometers. Then Uncle Raleigh came and said, look, you can make measurement, length measurement. Some of the physicists will forgive me if I make a slip in my statement. If you can measure it up to the wavelength or technically half of the wavelength. So if you are using a light of 400 nanometer scale, you can use up to half of the length accurately you can measure. But anything less than that, you cannot use optical light.  You say, look, don't tell me all this. We know about Bragg's law. We know what Bragg did. He used x-rays which were sub-nanometer and they were making measurements. Sodium chloride, lattice, the distances were measured using x-rays because they had a wavelength comparable to the inter-ionic spacing in sodium chloride lattice. So we know the difficulty in measuring in sub-nano, even in nanometer scale, there are technological developments that makes it possible for people to make measurements. So to look at atoms and molecules, that is where the challenge is for a chemist. You want to look at them in angstrom scale, if not sub-angstrom scale, 0.1 nanometer. So we need a method to measure them, technique to measure them. That is about the space. So we know already, you can use x-ray, x-ray diffraction, you can measure it to angstrom scale. You can also use high energy electrons to do electron diffraction and you can still make measurements of that scale. So space, in principle, that is how we measure. How about time? A train runs at a speed of 100 kilometers per hour. You can convert that into meter per second, 27.7 meter per second. Olympiad medal winner, not you guys. I don't know if any of you can run that fast, but you know who go to the other Olympic, the medal winner runs at a speed of 10 meter per second. You have to round it off. It is 9.8, 9.7. The challenge is to break that record every year people try. Now we look at the kinetic energy of molecules. This is, you see, chemists and physicists, olden days nobody distinguished between chemists and physicists. This made a lot of chemical discoveries. Chemists made a lot of physics discoveries and together they made a lot of discoveries in biology. But without making the distinction, if you want to calculate the average kinetic energy of molecules, so we used to learn the kinetic energy, average kinetic energy is proportional to temperature. We learned how to measure temperature, stick in a thermometer and measure and my teacher would say, you know, the proportionality constant is r. But I could never understand how they came up with the proportionality constant and p v equal to n r t. And how they come up with r, again I didn't understand, but we will not get into it. But what is important is that the average kinetic energy of molecules at room temperature, if you plug in the mass of the value for r, the mass of atoms or molecule, whatever, you can come up with a number like average speed of a hydrogen molecule at room temperature, it's about 1930 meter per second, right? That gives you a feeling of fast atoms or molecules or atoms and molecules are moving. But what is remarkable is that for a long time, today we are talking about observing reactions in space and time. For a long time, people didn't, they had to assume that, you know, there was Dalton's atomic theory, et cetera, et cetera. Chemists and physicists had this imagination that matter is made up of molecules, molecules are made up of atoms and they all had a lot of indirect evidence. With the indirect evidence, technology and science and technology was developing. Now, let us come back to the hydrogen molecule. See, a molecule of hydrogen in this room at room temperature moves about 1000 and odd meter per second. That's the speed with which it is moving. But left to itself, a hydrogen molecule is going to sit there and vibrate forever. Until you do something with it, it has an equilibrium bond distance. By now, you know about the bond length, right? The HH bond length in a hydrogen molecule is 0.74 angstrom and it has a bond dissociation energy, the energy required to break a bond. Depending upon the unit that you are comfortable, if you are comfortable with kilojoules, 457 kilojoules per mole. And a molecule that is sitting there and vibrating, the spectroscopy is used, a unit of centimeter inverse, which converts into that many cycles per second. So, in one second, the hydrogen molecule is making 10 to the power 12. That means the million square, million into million oscillations in one second. But if you turn it around, what is the time taken for one vibrational period? That is 750 femtosecond. This is 0.75 picosecond that comes to 750 femtosecond. So, if you want to observe a hydrogen molecule which is sitting there and vibrating and want to see it break, you have to do it within, intervene within this 750 femtosecond. So, you should use something to trigger the breaking within 750 femtosecond and you should do something to measure it within 750 femtosecond and you know the distances of this order, a bond breaks, so it should take longer than that and that is the resolution that you need. So, I want to set up, set the stage for you. So, if you want to observe a molecule breaking, we are talking about subhangs from resolution and femtosecond resolution, space and time. So, now, how fast do molecules react? Once again, you, I think by, since my two of my children went through high school and so on, I know what is covered, some idea of what is covered in your school book. This is rate constant. Rate constant gives you a measure of what is called a cross-section. There is a speed of the molecule that is the exponential factor given by uncle Arrhenius. So, if there is no react, no activation energy, they simply come, collide and react. So, you can set this to 0 and let the distance be an angstrom and the speed be 1000 meter per second. Actual speed is not so important. We are talking about the bulk part. So, the time taken for a reaction is 100 tons per second. I will show you, it is going to be even less than that. We are talking about the scale. Then you can use k, the pi, rc square, the collision radius of atom or molecule, the speed and that is the kind of a speed you get, what is called a rate constant. And you can, if you are used to moles per liter, that is the kind of a unit that you deal with. Now, already I have indicated, without explicitly stating so, what is a chemical reaction? I said there is hydrogen molecule sitting there and vibrating and it must break. So, bond breaking is a chemical reaction. If two hydrogen atoms come from far off in space and come together and form a hydrogen molecule, you have a bond forming technique. So, either you should have a bond breaking or bond forming or of course, you can have a combination of both of them. By the way, it is not so easy. Dr. Arvind Kumar can tell you, two hydrogen atoms, if they come together, they are not going to form a hydrogen molecule. They will come together and go back. All of you, you came to the Olympiad, saw each other, first day you did not talk to each other and then slowly you were introduced and then you form your friend circles. So, these two hydrogen atoms, if they come and go, if nobody introduces them, like they used to say about the Englishman, they did not talk to Englishman in a standard, in an island after shipwreck and they were not talking to each other because they have not been introduced to each other. So, these two hydrogen atoms must interact. How does interaction take place? Just coming and saying hello to each other is not good enough, something else must happen. You can have a metal, you can have a third body, which will take away some of the energy from these two hydrogen atoms and then they form a hydrogen molecule and then lots of other things. If you want to break up on, similarly, either you must shine a light or you must hit it with another atom or a molecule or a metal surface or whatever. So, most of the time you really come across a bi-molecular process.  It is preceded by a collision or a light or something, something, as it is, the molecule does not break on its own. A bi-molecular process is there beforehand. People will tell you, you cannot have a term-molecular process, very difficult to have three atoms collided at the same time. Invariably, there is a bi-molecular process taking place beforehand. So, most of the time, when people talk about various reactions, there is an underlying bi-molecular process. So, I said there is a bond breaking or forming and now the question is, when do you call a reactor and when do you call a product? Somewhere there is a change.  Then she says, better you have been to all the Olympiads and so on and you are still behaving like a child. You see, look, after all, I am your child. So, somewhere you transform from being a child, from a baby to a child, a child to a teenager, teenager to an adult, adult to an old man. Some of us in this room would not like to admit that we are old, somewhere along the line we have become old men. So, there is a transition. It is not a sharp line. This you must understand. If you have understood this, then my lecture is justified. So, somewhere there is a transition. See, what is obvious today are not so obvious in the early part of history of science. So, somewhere a reactants transform into products. Two hydrogen atoms come together and form a hydrogen molecule. Somewhere they become a hydrogen molecule. A hydrogen molecule breaks into two hydrogen atoms somewhere along the line. H2 molecule faces to be an H2 molecule. It becomes hydrogen. If you bring a hydrogen atom and a deuterium molecule and form a new bond and break the old bond, somewhere along the line the new bond is formed, somewhere along the line the old bond is broken. Now, you can go on giving examples but the point is made. So, reinforcing it here. So, this is a reactant and that is a product. This is a hydrogen gas. For example, hydrogen gas and chlorine gas and here it is hydrogen chloride. And somewhere along the line the transition takes place. Now, how do you identify the transition state? How do you define a transition state? When I look for you, they receive you at the railway station. Father writes ourselves uncle or auntie. He comes to the other station. Please receive him. He is going to HBCSE or at the airport. Wherever they want to know I have not seen your son. It is kind of photograph. Today, of course, technology makes everything possible. Over my days, it was not so easy. You will say, look, one boy if he is hesitatingly coming as the last passenger out of the bogey then he must be my son. They have character. So, structurally, dynamically you must be characterized. So, here is a reactant and here is a product and somewhere along the line it goes through the transition state. I do this picture. See, this is a happy phase. That you know is a grumpy phase. Everything else is unimportant. The nose, two eyes, et cetera, et cetera. The gold wall of face or a lumbar wall of face. The difference between a happy phase and unhappy phase is this curvature. Is it flat? The guy you cannot tell whether he is happy or unhappy. So, I just used it as an example to go from a grumpy phase to a happy phase. You go through this whether you like it or not. That is what happens. Wigner, actually people, when you go to further, you will learn about Eirings' transition state theory. But about the same time, Wigner, all these faces will swear about Wigner and his work as a physicist, but he was a chemical engineer and he did his PhD with Michael Pallani, who was a chemist at that point in time. There is a reason why I say that time he was a chemist because earlier he was a doctor and later on he was a philosopher. So, as a transition state for him, for a medical doctor to become a philosopher, he went through the transition state called a chemist. And he did a lot of outstanding work which would have gotten him Nobel Prize at some point, but didn't happen. That's a different story. So, Wigner did his PhD with Michael Pallani in chemistry. So, he says the transition between the two regions forms the reaction.  There is a transition. It's a behavioural change.  Same thing happens outside the compound wall. Two people walking together, talking to each other and suddenly they pick up a fight. There is a group fighting with each other. So, you go from individual behaviour to social behaviour. There's a transition. Each one of them can be looked at in the same angle. So, the concept of transition state goes beyond chemistry. Incidentally, there was an article by Sushantop on Sahas' ionization equation. How many of you have heard about Sahas' ionization equation? Meghna Sahas wrote about this several years before these guys wrote about the transition state. But whatever formulas these guys were using from statistical mechanics, Sahas was using it ten years ahead of time. So, he was looking at the ionization process an atom, an alkali atom, an electron is removed. So, ionization takes place. Somewhere there is a transition. Assume, tautically, there is an alkali, a sodium cation and there is an electron. Together they form a sodium atom. So, how do you calculate the rate for this? So, Sahas came up with this formula based on equilibrium statistical mechanics. Properties of the cation, properties of the electron in the form of what is called a partition function divided by partition function of the neutral ion and he could come up with the rate equation. Fantastic. And he didn't use the word transition state. The concept of transition state as chemistry introduced it was yet to be done. Ten years later that would come. Some of these people are considered great leaders. They have that insight into problems. They come up with the methods. They wrote even in a flow where there is a viscous plastic flow that can be described as a chemical reaction. But for our purposes, it is a bond breaking and bond forming and a molecule that constitutes a chemical reaction. So, here is the illustration. Potential energy versus distance. This portion is how a harmonic oscillator looks like. It simply sits there and vibrates. Everybody knows about harmonic oscillator, right? So, the oscillation takes place. But somewhere you must make it an harmonic and break. So, this is where the somewhere they become. So, where do you decide? Some people operationally use it two times the bond length, right? If two people are walking together, they are friends. If they are walking on the other two sides of the road, then something has happened. These guys are not talking to each other. They used to be palped in the chemistry olympiad. Now, the distance between the two is decided by the size of the pavement, size of the road or size of the highway, right? But the fact remains that they have no longer friends. So, here it gets a little bit more complicated. A hydrogen molecule sitting there and vibrating, when another hydrogen atom comes in, this starts loosening. This is like, you know, two people who are good friends. A third person comes and once in a while, he is not listening to him. He is looking at him or her, whatever the case. Now, slowly the old bond loosens and the new bond begins to form. This is a fundamental question. What is the energy required for this process to take place? One is simple. Break the bond and form a new bond. To break a bond, you have to spend a lot of energy, 100 kcal per mole, 400 kilojoules per mole. 1931, Michael Polany wrote in a small book called Atomic Reactions. You can Google Atomic Reactions with Michael Polany, you will find. It is not surprising that, you know, what he says is surprising that you spend 10% of the energy in 100 kcal per mole or 400 kilojoules per mole to spend 10% and the reaction takes place. So, the new bond is paying for the old bond breaking. That is the idea. But how does it take place? You have to define a transition state. You have to define a path. The path in which, for a simple diatomic molecule, it's very easy to define. This is the path in which the bond is breaking. But if you bring a third atom from here or here or here, now you need three dimensions. If it is a DNA molecule where the base pair is separating, while the rest of the strands are intertwined, right? You focus attention on it. One of the old-timers in chemistry said, look, all reactions can be modeled with either a three-center or a four-center reaction. It doesn't matter how big the molecule is. A handshake takes place between two persons, right? All you require is two hands. After the fight, everything is over.  Of course, if you are in Modi, you do a hug. It requires a little bit more degrees of freedom. But this is good enough as a symbolic point. So we are talking about going from a reactant valley. See, when we talk, we introduce many terms. I have already, in your mind, put the concept of a valley and a product valley. If we have talked about valleys, if you have hills and valleys in the mountainous terrain, in a flat surface, there are no valleys, right? So one is already anticipating some kind of a mountainous terrain where there is a reactant valley which makes a molecule sit there and vibrate and a product valley where the molecule sits there and vibrate and somewhere you go through the transition. And we must do it in the most economically possible way, energetically economical way. So this is where there is an atom and a molecule and they come together and they come on the other side as this. Like you go to the movie, right? A boy and a girl goes and another girl comes. After the movie is over, this boy is coming out with the other girl. Just something like that. So somewhere along the line, there is a transition taking place. This is the contours.   Every point along this line has the same height in a geological contour map. In this case, they have the same energy, less energy here, less energy here, less energy here and something happens. So you go from the reactant valley to the product valley and at every stage you look for the minimum energy. This is how the molecule BC is oscillating and this is the minimum point and as you go as A comes closer and closer, this BC is now oscillating slightly differently with a less curvature and at this point it switches over to the product. So this dashed line is idealized to pass. No reaction ever takes place through this path. It took a long time for me when I started as a PhD student. I had a lot of difficulties in understanding these simple plots but if you understand, I am happy you understand. If you think you understand, I don't blame you. This is the cross section. If this is reactant, this is product, we go through this line. In a symmetric case, the hydrogen, hydrogen is very easy. This side is reactant, that side is product. This is the dividing line. If you look at the energy along this dividing line, along this line it is a maximum, it is a barrier. In a mutually perpendicular direction it is a minimum. The saddle point by definition is a maximum along the reaction path and a minimum along mutually orthogonal position. It was called a saddle. I was telling Ankush, before coming here, I decided I will better have a picture of how many of you have not seen a saddle? Every one of you have seen a saddle, wonderful, whether you sat on it or not. That is the minimum in this direction and maximum in the opposite direction. While looking for a picture in Wikipedia for a saddle of a horse, I learned something new. This is the mountain called saddle in Scotland because you see that looks like a saddle.  A couple of years ago, my wife and I went to Sihachan Glacier without knowing if we are in Sihachan Glacier. Once we reached there and found it was Sihachan Glacier, we were excited because that is where a lot of this cargill war and all those things took place. We had the privilege of having lunch with the army people. While standing there while on the way, I just went on clicking pictures because every little thing here reminded me of a saddle. This is the best picture that I chose from that collection and you can see that is a saddle. This is a saddle in Sihachan Glacier and if you are here and you want to go to the other side, clearly you can see the road by which you go. That is the road in which the army jeep went and we also went around but if you are a common man or you are riding a pony or you are a buckery goat, the goat will not go and look for this. The goat will simply climb over here and it just goes over this minimum path that is the saddle. Now what is important is now to translate this into a formalism, calculate rates, make observations and if your predictions and observations match, then you know that your theory is good and your experiment is worth. This is just a definition of it in one direction, it is a maximum, another direction it is a minimum. The energy of this point is what is called the barrier height that is approximately would correspond to what Arrhenius would call activation energy. I will give you a few examples that is a simple example I have been talking about hydrogen atom and hydrogen molecule, it is a neutral. The old bond broken and the new bond form they have the same energy, no energy gain, no energy loss, neutral. This is a case where H2 is broken, HF is formed, it is a highly energetic reaction exothermic. In the reverse direction it is endothermic. This is a reaction I spend lot of time about 30, 40 years of my life studying this one reaction but we will not get into it. The Sun Polani came up with a set of rules, we will talk about them in a few minutes. This is the original potential energy surface that was devised by London. He gave the formalism. How many of you have heard about London equation? Because at the high school I do not expect you to hear about it. I ring equation have you heard? I ring transition state theory you have heard. I understand you had a exam paper where there was a the transition state was introduced and the author of the paper. So this is how the original potential energy surface looked like. Do not worry about that. What is important is a 3D visualization of it. And this is the old paper of 1930s. Again what is important here? For you it is not important. When you go to the higher levels BSE or beta or whatever you will see there is a situation where you use a coordinate to consider a 3-particle motion into a 1-particle motion. This is the 1973 when I was doing PhD. That is how the potential energy surface got modified. Improvement in calculations and our understanding. This is the best surface that is available at this point in time. This is for an exothermic reaction. A fluorine atom collides with a hydrogen molecule comes out of the hydrogen fluoride. Somewhere here is a saddle and you see something very striking. This is the reactant and the saddle is very close to the reactant. The barrier for the reaction is very small. So in this case this transition state resembles the reactant. Look at the picture in the reverse direction. So now you go from here to here. You have to climb up the barrier and reach the saddle now close to the product. So in this case you say the transition state resembles the product. In this case the transition state resembles the reactant. Whenever you one of you have a bond your javima would say the nose looks exactly like his grandfather. His eyes look exactly like grandmother. Just how people describe. So you describe the transition state resembling the product or resembling the reactant. And this is very typical of exothermic and endothermic reaction. In the case of exothermic reaction it resembles the reactant. So people use the same method to study four atom reactions. So when this paper was published in 2000 that is when one of the old timers said look if you can study a four atom reactions that means you have learned to study all reactions. Now what are these Polani rules? The father Polani had certain discovered certain things and the son Polani carried forward the ideas and made measurements which are not possible in father's time and found out something very simple. If the saddle point is in the entry channel or if the transition state resembles the reactant then translation is effective in crossing the barrier. You know many reactions that you study for example go back to the same old curd you make the heat at home in winter time the heat doesn't become a curd. So your grandmother will say but you put it in a little bit of a hot water keep it warm for 2-3 hours it will settle. Summertime no problem it forms a curd by itself within a couple of hours and if you don't take it out it becomes a sour. So there heating is effective but there are reactions where heating is not effective. If I want to go this way out of the room my momentum should be in this direction if I keep oscillating in this direction it doesn't matter how much faster and faster I vibrate in this direction or keep pacing up and down in this direction it will not help me to go across this door. So if you want to get out of this door your momentum should be in this direction if you want to get out of that door your momentum should be along that direction. What is seemingly so obvious and simple for exiting in a classroom was not so obvious in the case of molecules. So what this gentleman Pallani did was to find show if for an exothermic reaction very counter intuitive the energy is released by the reaction if you want to make that reaction go faster increase the temperature and what happens then the product molecule is vibrationally excited. This was a fundamental discovery if the product molecule is vibrationally excited and if we can catch it when it is hot and let it cool cool in a coherent fashion you will have a laser. So this would be a case so this formed the basis of forming a chemical laser. He was a starting faculty member University of Toronto 25-26 year old and he said look if you observe the exothermic reaction and catch it technology was needed to make this observation of a infrared proton being emitted by this freshly formed product he said you should get infrared chemiluminescence and years later he put together a lot of data he and his students and came up with this picture this reaction energy is released hydrogen chloride is formed this is much stronger than this bond a lot of energy is released it is released in exothermic reaction it is predominantly a lot of it is present in vibrationally excited when compared to the ground state that is the ground state 0 energy lot of energy goes into vibration in comparison very little energy goes into rotation this is a triangular plot this is zero energy in vibration this is all the energy is in vibration all the energy is in rotation all the energy is in transition if all the energy is really completely in translation the points will be on this line. All the energy was in vibration, they will all be there. If all the energy was in rotation, they will be there. So, what they found out was, there was a substantial amount of energy in vibration. Then he wrote a small paper and said, if first of all this is called a chemiluminescence, chemical reaction emitting a light, the you know, the firefly that you see is a bioluminescence. It is a chemical reaction taking place in a biological system, light coming out in visible region. In this case, chemical reaction emitting light in infrared region. This chemical laser, this chemiluminescence, if done in a coherent fashion will result in chemical laser. So, he and his head of the department went to the university lawyer and said, we must patent it. You know, today you hear so much about innovation, entrepreneurship, patenting, etc. People will tell you, there is not enough to do science. You must do science which is useful to society. You must convert. Now, if you go to Aysar Mahali website, it will say, in pursuit of knowledge. So, I told somebody, you know, our goal is in pursuit of knowledge. He said, beta, you must convert knowledge into wealth. That is what everybody does. You also must convert knowledge into wealth. So, this young man and his head of the department went to the lawyer and said, we must patent it. I told him, why do you want to waste your energy in patenting it? So, they came back. They did not patent. But somebody else said, look, if that is the way to form a chemical laser, I will form the chemical laser. So, when that is in one direction, it went. So, chemical lasers, when you hear about Star Wars, right, about 20 years ago, it was very fashionable to talk about Star Wars. A lot of basis of those Star Wars speculation was based on chemical laser. You just simply add up more and more of it, and then you can destroy almost anything that you want. But when Polanyi was describing this discovery to another scientist, he said, you know, if energy is released in the form of vibration, now you work backwards. It is a principle of microscopic reversibility. My daughter used to sit and watch TV almost every day and watch this Mr. India movie. See, there is no more. Hey, have you seen Mr. India movie? Anybody in this room who has not seen Mr. India? Right? You have not seen. See, see it sometimes. It is a fun movie. There, Anil Kapoor tells C.J. which was looking for an apartment. This staircase takes you upstairs and the same staircase will bring you down. That is the common man's way of stating principle of microscopic reversibility. If energy is released in the form of vibration, in the reverse direction, vibration should be helpful in forming the product. So, that is what they infer indirectly. Make a molecule vibrationally excited. The reaction will go faster, not necessarily by simply heating with the Bunsen burner or with the electrical heater. And then they showed experiments will not go into the details of this. Oh, this is an important one. On the other hand, you decide to make the reactant molecule rotate faster and faster. In this case, go back to this example. If I want to get out of this room, my momentum should be in this direction, not as a vibration in this direction. And there is an help if I can keep on doing this rotation faster and faster. Right? I do not get out of this room. I stay inside the room. I simply rotate faster. It does not help my reaction. And sometimes it may even be in unhelpful. Rotation can inhibit the reaction. Now, by looking at all these things, Michael Polanyi got his Nobel Prize in 1986 along with Herschbach and Lee. But all this concept of a transition state predicting, observing what happens in exothermic reactions, what happens in endothermic reactions, they are all indirect inhibitors.  Then somebody says, ah, somebody punched you in the nose. You have not seen somebody punching in your nose.  For all you know, you might have tried to hit a mosquito and then you hit many things that happen. But he infers as to what must have happened inside this room. So, these are all mounting to indirect evidence. But people are not happy. I knew John Polanyi was excited about it, wanting to observe the transition state. Agama Jail was not in this business explicitly. He also joined. They wrote a paper called, Holy Grails in Chemistry. What is something special you must do in chemistry? They said, we must observe the transition state. This was in the 80s. Father Polanyi had done a lot of alkali flame experiment. This is Michael Polanyi, alkali flame. You Google, you will get all the details. So, the son Polanyi said, look, if I look at this reaction, this is sodium atom. The normal yellow light that you see in a sodium lamp, in a physics lab, we used to measure the wavelength of a sodium lamp, sodium light. If you observe when sodium is just being freshly formed, you will find a slight shift in the yellow light. You know, these people who have interest in astronomy, astrophysics, they make their living out of measuring the shift, right, Hubble's law, red shift in the, in the emitted light, expanding universe, all that stuff they talk about. All that depends on the shift in the wavelength. So, these people said, look, you must observe the shift in the wavelength. It will be a million times weaker signal. But if you look for a signal which is million times weaker, you will find the wings. And they found the wings. But Jail took a slightly different route. This is where, when a freshly formed sodium ion emits light, sodium deline emission, but when it is being formed, in the process, the emitted wavelength, light can have a different wavelength. And by looking at the shift in the wavelength, you can find out the forces that is the difference. A little complicated way of doing things. And they found experimental evidence for it. One, a million times weaker signal when compared to the sodium deline, Ahmad Jail said, look, I want the record. Let me just see. Go ahead and see. Put a CCTV camera inside, CCTV, what is it called? CCTV, no? You put a camera inside the room in the auditorium, we will know who punched, who knows, right? Direct evidence, make the observation. So, he decided to do this. And that is how the femtosecond chemistry came. Many of us who are studying these problems theoretically using computers had studied the change in the bond distance. When atom and a molecule come together, this atom is coming in closer to this, and this small atom is leaving. So, you just measure this distance and this distance, and you can tell whether the reaction is taking place or not. This is decreasing, and this is increasing. Somewhere here is the transition state of the order of a few femtoseconds. But if they are ionic species, they hang around together to go or not to go, to go today, to not to go tomorrow. They keep on doing this. They spend a lot of time out of picoseconds, a thousand times more time. So, Ahmad Jail said, look, let me look at a reaction hit with a photon and watch the molecule falling apart. This was ICN molecule. He broke, the CN remains intact, the cyanide group remains intact. The IC part breaks, and he was able to observe this in femtosecond time scale, and then he recorded evident. And what he did was to pump, you put energy and pump it into this tape, and then as it is falling apart, you probe this. Use another laser to measure this energy. It is called a pump and probe experiment, and you do this in real time. Say, in terms of a real time, 200 femtoseconds he was able to make the measurements. That was a fantastic one. You know, really progressive experiment, but then he did one more experiment where they were looking at sodium iodide. The sodium iodide, the atomic molecule, you know, sodium is Na plus I minus, sodium chloride Na plus L minus, the old experiment x-ray diffraction of common salt. We know there are ionic species there. But when you have a gaseous sodium iodide, sometimes it behaves like a new covalent molecule. Sometimes it behaves like an ionic species. So, you can look at the transition between the two kinds of behaviors, and you can pump light and make sodium iodide into the excited state. When it is in the excited state, it leaks. A part of it leaks and forms a covalent species. The remaining portion will go back. So, this goes back and forth oscillation. This back and forth oscillation will go on decreasing, because every time there is a small amount leaking. It will stay about 10 percent leaking. So, 90 percent, 90 percent of the 90 percent remaining is 81 percent, 81 percent, 90 percent of 81 percent is 72 percent. So, this signal goes on decreasing in height, but the distance between the peaks in time, time difference between the two, tells you the vibrational period. So, he was able to demonstrate experimentally the vibrational period of sodium iodide. He also did it for iodine molecule, not only vibration, but also rotation. So, he was able to do this experiment. This is the principle of pump and probe. You bring a laser beam, you put a beam splitter. Part of it goes and pumps the sample, and the part of it goes through, and it goes through various materials, and it undergoes what is called a harmonic generation. The wavelength gets shorter and shorter and shorter by multiple, 2 times, 3 times, double harmonic, triple harmonic, 100 times harmonics, whatever. So, if it is a visible light, becomes ultraviolet, ultraviolet, even then it goes into x-rays. So, the wavelength that is coming out here to probe can be several times smaller than the original laser. Now, what is challenging was the distance traveled by this laser and this laser is of the order of a micron, if you want to measure in femtosecond. Normal spectrometers depend upon several centimeters, but here the difference between the two path lengths is a micron, approximately. And if you have to put it through another non-linear sample here, and for it to come out, time wise there is not much of a problem. It is a distance, this is extra distance that you have to try. What was important was he said, look, if this light that comes out here can knock an electron out, do not let the electron go, let the electron take a picture of the molecule, it is like a Modi taking a selfie.  Now, first it gets tricky to do this experiment, to make the observation and one molecule, one electron is not enough to record the even, you must have several of them. So, it may not be, it may be electron coming out of one Modi, but taking a selfie of another Modi, because they all look close. The reason I put Modi as an example is, today this is common, you see several pictures of Modi face everywhere, and everybody, how many of you have, who has not taken a selfie so far in this room?   Before that, he was trying to see if he could do this and take a picture of a DNA double helix and zipping in real time and space. It is like you change your bunion for whatever advertisement you are doing, Shah Rukh Khan, somebody or Salman Khan, removing the bunion for a picture, that is how much money he makes by removing the bunion, take a picture of it and that guy probably makes a living by eating roti sabji on the platform, does not matter. So, what is important is what has been possible, femtosecond, I said people like me said look, femtosecond is where chemistry takes place, bond breaks, bond falls. The physicists would not stop with femtosecond, they want to develop atosecond, and they develop, technique has to change, methodology changes. We said oh, atosecond can be used to knock electron from the core. So, you can do ionization, core ionization spectroscopy, you can knock electron out of the core of an organ atom and do the measurement, physicists were very happy. People like me said look, there is no fun, but we did not realize when you knock electron out using this atosecond pulse, uncertainty principle tells you delta E delta T is greater or equal to h bar. If this is 10 to the power minus 18 seconds, I leave it as a homework for you to find out delta E, that energy spread is enough to break a molecule, is enough to take an atom or a molecule from the ground state to several excited states, which means you have a chemical reaction now taking place not from the ground state, but from a variety of excited states. Each one of us behave differently, but under different conditions. All these behaviors go into one and something comes out. Then we have to figure out, later on we will figure out as to which one of them came when it was Shant Surupi, when he was angry mood, when he was in a crazy mood, many things we do, but as a matter of analysis. But what is important is to realize, now we are talking about a different chemistry, it is atochemistry. We do not know the details. Some of you, when you go to higher studies, maybe one of you will do atosecond physics, maybe one of you will do atosecond chemistry and whatever results you get, send me an email, answer them at gmail.com, that I listen to you on that day, I have done this atosecond physics chemistry or biology and this is what I have found and this is going to change history of, the beauty of science is that you ask one question and you answer and this answer raises some other question. And you keep asking this question and science grows.  How many of you have not seen the journal called the resonance? You have not seen. All the medallists get the subscription, right? I will find out. Earlier the tradition used to be as KVP scholars get and earlier the medallists used to get a copy of one subscription of one year free from the academy. I will request Ankush and the coordinator to send me a list of the medallists and we will arrange to send you a free copy. But this journal meant for undergraduates, meant for people like you. This is the January issue of it which gives a picture of Michael Polani and the potential energy surface. It tells about Michael Polani, how as a doctor he was writing papers in chemistry and as a chemist how as writing papers in philosophy. This is the next issue, it has not come out yet. Just yesterday I saw the cover page of this magazine, the journal. About ten years ago, about eight, nine years ago, Joel and Thomas wrote a book, 4D Microscopy. I was curious, I bought a copy, I paid $15, got an e version of the book and started reading it. I didn't realize the importance of this. But when I was preparing for this talk and I was editing this issue, I realized the significance of observing chemical reaction in space and time by doing 4D Microscopy. So his contribution is described in the next issue. So it's available free. So you are all Google generation. You Google resonance, you go to January issue, you will get articles about Michael Polani. Wait for ten days. Today is 12th of June, it will be out. June issue will be out. You Google resonance, June issue, you will find whatever, certain things that I have talked about there. And I want to, it was shot by extra another five minutes or so. I want to thank Angus for asking me to come and share with you excitement of whatever I describe. Thank you. Thank you, Professor Satyamurti. We can take five to a few questions for next five to ten minutes. Any questions for Professor Satyamurti? So in the diagram when we were performing 4D Microscopy, we were using one laser source and we were separating it using a beam splitter. So and when we use this harmonic amplifier or whatever that is called. So why is it necessary to use one source and if we use say one source for directly sending light into probe and one for you know low wavelength light, we don't have to worry about the path length thing. So why is it necessary to have one source? Yeah. I punch in your nose and take a picture of him. You understand the difference? Yeah. When I punch in your nose, somebody should, I should take a picture of my punching your nose in real time and space. Right? If you don't do a beam splitting and use some other light, unfortunately this picture does indicate what you are indicating. See here is a little light. You are not able to see it or not bright enough. Here is a little photon. It's a baby thing here. The photon which excites the molecule which is breaking apart and breaking apart. It is another part of this photon which generates an electron and takes a picture. That is why it is a selfie. You punch, sometimes you see in the movies that the fellow punches his nose himself and then goes out and complains that he punched my nose. Right? But you are not interested in proving somebody else. You want to show how you punch your nose. What is it? Blue whale, right? How many of you have heard it? Yeah. I would have been happy in this case if we did not know about it.  Right?   Right? So, this is a case where you want to excite the molecule and you want to take a picture of it breaking its bond or forming a bond. So, it is there. That is why the beam splitter is necessary. Otherwise, they are independent. That is not a big deal. So, in the pump and probe setup, you mentioned that the probe wavelength is shorter, right? So, that will have a higher energy. Why does not that cause the reaction instead of the probe bubbles? Yeah. It is a very, very, very good question, very important question. When George Porter did the flash photolysis, it was a pump and probe using the same light. But later on people found, like in this case, the purpose was not if we just simply did the pump probe experiment. See, I mentioned that some people were critical of saying what was so special about Ahmad Zewail doing experiment. Kinsi in MIT was one of the pioneers in pump and probe. So, here you see there is a pump and there is a probe. They were using two lasers to do the pump and probe. But you want to record certain even, then you have to change the wavelength. That is when it becomes a spectroscopy. In this case, the purpose was not just to do a spectroscopy of the transition state, which was the original experiment that people were talking about when they were talking about the Holy Grail. But what Zewail did was to go one step further. And let me take a picture of the two of a selfie of a molecule. So, the physicists will tell you how they would talk about a single photon interference. There could be a single photon interference. There could be a single electron interference. Definitely single X-ray photon interference. But these are new answers. I don't, if you ask me further questions, I will say you please ask these people. But what is important is, but you have clones. It is a, let us say, ozone molecule falling apart, not just one of this one, several ozone molecules. When people talk about a single molecule spectroscopy, they don't really mean single molecule. They are making observations of a set of molecules and there is a certain behavior which can be attributed to a single molecule. So, to take this into space and time, the probe has to be of a different wavelength. Sir, if we are observing the molecule in any container, then obviously there will be many species, millions of reaction pairs going on at the same time. So, how will you focus on a particular means of reaction thing? It is possible that the focus changes. See, when you see Shahrukh Khan jumping over the cliff, he actually doesn't jump. It is a stuntman, stuntman who does it. And he may or may not actually do the jumping. You produce different frames and then you do the editing. So, this is what happens. So, when we want, when we say observe a molecule, remember they cannot be distinguished. You cannot tell one ozone molecule from another ozone molecule. By definition, they are indistinguishable particles. They have a collection, collection of non-interacting molecules. It is important that they are non-interacting. Otherwise, they will start interfering with themselves. So, when we say single molecule, we actually mean getting the property of a single molecule from a collection of non-interacting. A little bit of, it's not cheating, but a little bit of a cheating in the language or in the description. Go for the questions. I thank Professor Satyamurthy for this lecture. And we have a short key break. And then we gather back around 11.35 for the valedictory function. Thank you. Thank you.


Oh my goodness! Oh my goodness! I woke up this morning, checked my email, and Ulta is having a humongous sale on so many things that I love that I wasn't even planning on doing this video, and I had to sit down and do it for you right now! Hi friends! Okay, I'm beyond excited. Can you tell? I sat down, opened my email, and there is all of this makeup on sale for the Black Friday sale at Ulta. I do have some other things to tell you about, but thus that is why the hair is straight. All I got to do to it today was just use my hairdryer on it, which by the way, I wanted, hello, I wanted to share with you this cool new dryer I got. Okay, it looked so much like the Dyson that I'm like, I know that I probably will never be able to afford the Dyson. This is an Ionic one that I got off of Amazon. I got it because when I go see my daughter, my huge one is like a nightmare to put in my case. This one is super light, and it's really easy. It only has three speeds, but it has a cool shot too. It wasn't too hot, even on high, which was great for me. And you can hold the button and just have a cool shot, which is what I do most of the time when I'm doing my hair, so it doesn't get fried. But this dried my hair so quick. I mean, I jumped out of the shower this morning because I wanted to get this video going, and it just dried my hair so fast. And I am really enjoying that. And it's not very expensive either. So I wanted to make sure I shared that with you. Let's talk about what's going on at Ulta. First of all, one of my favorite foundations ever is the Tarte Double Duty Beauty, the Face Tape Double Duty Beauty. And it's the one that has the purple on the top of the, and it's no, it's not because it's purple that I bought it. It's a really good foundation. It's what I have on today. It just covers really quickly. It's very easy to blend out. And I have mine in 22N. This is going to last all day long. It's going to look fresh. It's not going to look flat or matte or dry. It's great for those of you that might have skin that is a little bit, you know, normal to dry, maybe a little bit combo, because I do kind of get a little normally on a normal day. I'm going to get a little bit oily through here, but this doesn't show that up. So I love this. It's one of the ones that's on there. There's also one that's called Found Sealer on there. And it is one that I just barely ordered myself because I have been hearing great things. I got a hair. I've been hearing great things from people about it being really good for mature skin. So I'm going to try that one. And then of course, the Tarte Amazonian Clay. This one was on Ulta's 21 Days of Beauty and I picked this one up too. And let's see, what did I get? I got medium beige and I think it's a little bit dark, but I can put it into, you know, I put my white mixing medium in it and it's a really good color for me. Actually, if you're an oily skin gal, combo gal, you're going to love this. If you're somebody that has dry skin, if you want to put a drop or two of oil in it or a drop or two of hydrating primer in it, it works great, especially during the winter months. I find that in the summer, I love this just all by itself. But when I'm a little bit drier and the dry heat comes on inside, I'll go ahead and I'll just use this one with a little bit of extra in it, maybe some moisturizer or something. But it's great. If you wanted to make like a tinted moisturizer with this, this would be perfect because it has such great coverage. Okay, so then they had all these mascaras on sale. Once that they have on there is the Benefit Roller Lash. That is my mom's, a very favorite mascara because it holds her curl and she has very straight lashes and she loves that one. Tarte Man Eater. Now, this is the one that I have on today and I love it for building up my lashes. It does just such a good job for volume and, you know, I'd use a lash serum, which I will make sure I link below. But the thing is, is that they get long, but they don't necessarily get thicker and that one is really great. So Tarte Man Eater is a great one. I like the Urban Decay Perversion, which they have on here too, but it doesn't wear as well. And then the It Cosmetics Super Hero, that one is so many people's writer diets, a tubing mascara. And if that one is one that you love, then definitely jump on it. I've heard so many good things about it. Clinique High Impact. I actually just bought one of those to try. So I can't really say yes or no. If you guys know of any of this stuff that's on sale and you have tried it and you love it, just let everybody know down below so we can kind of hop on that train. So yeah, I'm going to try that one. Buxom. I love their lash volumizing mascara. I love that mascara, but it doesn't do well on my bottom lashes. I don't use anything on my bottom lashes except for a waterproof mascara because otherwise I get smudging. So I use the Benefit They're Real and I also use any other that is waterproof. That says it's waterproof. So just so you know that these mascaras are the ones that I use on the top. All right, so moving on, there's all kinds of lippies on sale. I'm so excited about this. Okay, I have the Bare Minerals Gloss. This one is the gloss, I think. Anyway, this one is on sale. This is the Gloss Balm. And that's the one that I have. They don't have this color, but this consistency is so nice. And so if you've been thinking about doing some of these, see how it's really nice and got a little bit of color in there. This one is, they don't have it there, it's called Love. So I don't want to mislead you until you can get that color, but they do have 15 colors in it. Really wanted to share that one with you. Kylie Cosmetics High Gloss. I've never tried one of those. I am going to try one of those. And then they have the Gen Nude Matte Lip Color from Bare Minerals. Lime Crime has theirs. Bare Minerals has their lipstick on sale for $10. NARS has their lip gloss on sale for $10. I love NARS lip glosses. They're so nice. Never tried the Tarte Sugar Rush. That one's on sale. There's so many in here. There's so many. Smashbox has their Be Legendary Prime Pencil on. And I hadn't tried that one before, so that one's going in my cart too.  The Anastasia Beverly Hills Glow Kits, those are 50% off. And then Lawn Comb has their Sills Booster at 50% off. So it's $13.50.  I'm going to try it again. I don't know whether or not it'll be good for me, but I'm going to try it. And then the MAC Select Studio Fix, it looks like their pressed powder, some of their foundation, that kind of stuff. That whole line of base makeup. I actually just purchased the MAC Studio Fix because Lisa Jay was talking about it and she did a demo. And I wore it over the weekend when I was out of town. And it's gorgeous on my skin. I love that stuff. It's just it. I wore it twice. It lasts all day long. It was beautiful. Bobby Brown has her long-wearing cream shadow sticks at 30% off. I thought that was really good. Jaclyn Cosmetics, I haven't been able to get much of her stuff, but her bronze and blushing duo is, let's see, that is 50% off too. IGK is 50% off. That is such a good brand for hair. I love that. Nude Sticks are $15, $15. I just bought one at the Sephora sale for a lot more than that. And then Holiday Kits at MAC are 25% off, Estee Lauder Primers, Christa Ness Hair and Smoothing and Styling Set. There's so much on here. I can't believe it. Anyway, there's tons. So go over there. I will make sure that I link as many of these as I possibly can for you. But I'm super, super excited about the MAC ones. Oh, I did want to tell you, MAC lippies, a lot of them are like $15. I want to show you my very favorite lip gloss. This is what I have on today. This is my very favorite lip gloss that they've had forever. This is called Oyster Girl. It is a combination of a shimmer with pink and peach, a duo chrome part of it. So dang pretty. I love it. And then their lipsticks. I have so many of their lipsticks. I love MAC lipsticks. I've been a long time lover of MAC lipsticks. First one is called Cream Cup. Most of these are going to be pink, just so you know. I'm the pink girl. This one is like a peachy pink, but it's a super light nude. And it's the one that I have on underneath the lip gloss with a lip liner that I got from, I think it's from Sephora. I think it was Sink or Swade is the lip liner I have on. I'll make sure I link that. This one is called Brave. This one is new to me, but I'm excited for this one for fall. I just think that that is a very pretty neutral pink. And then the next one is called Creme de la Femme. This is my OG lipstick that I have worn for years and years. This is a definite mauve with a little bit of shimmer undertone under it. And then this one is Plum Daddy. Again, this is one I've worn. I can't tell you how many times I've worn this one. Not Daddy. Plum Dandy. Plum Dandy. Okay, this one has just a little bit of a sheen on top of it that reflects just a tiny bit of peach. No glitter in any of these. I'm not a glitter lipstick person. And even the lip gloss, no glitter in it whatsoever. This one is Angel. This is one of my very favorite nude pinks as well, because it's super light. It's a little bit different than Creme Cup. If you see it right there and then Creme Cup's over here, you can tell that that one's just a little bit more pink. And then Fabby, this is one of my favorites as well. I'm having a hard time running out of places here. You can tell that I'm a pink lipstick person, but each of them, believe it or not, when I'm here looking at them, they do have a little bit of a different look to them. And then the last one is Creme De Nude. And Creme De Nude is one that I bought recently because I wanted it to go in the middle of my lipsticks and give kind of a glossy pout to it. It's just a very, very nude color. I actually think I heard about that one from Tati. I also absolutely love snob. I couldn't find snob probably because it's in my car and I wear it all the time. Snob is like a bright blue pink. So you know that. So I'm going to be picking up some more of the lipglasses. That's the only lipgloss that I have. I absolutely love it. I love the way that it wears. I love that it stays on, but it's not like a really tacky lip gloss. So I'm excited about that. Before we jump off of the Ulta Train, I just wanted to tell you guys that I did purchase the Tarte, the Tarte Lit Full Bloom palette. This does have that cocoa smell that Tarte is so famous for. So it does have that. But I think this is so pretty. It's got tons of lighter colors. And I know it's probably looking really light from where you're at.  The rest of it, I think, is gorgeous. What my one complaint is is that the shimmers aren't shimmery enough or bright enough. Now that should be kind of a plus for most of you. Most people don't like to wear super bright across their lid like I do. I love wearing super bright colors. So I can get away with like putting this color down and then putting one of these on top of it. But I'll show you what I mean. It's, you can tell right there, see it's not like super in your face high beam, the kind of thing that I normally wear. It's gorgeous. And this is going to be a beautiful gorgeous everyday palette. So I wanted to make sure that I told you about it. It's the quality that Tarte has is there. This is what I have on my eyes today so that you know that except for on the lid right there. I did pop a little bit of highlighter just on the lid just so that you understand that in my inner corner and my lid was not in this palette. But I did put like this color right here, which is a beautiful, taupey shimmer color. These shimmer colors, they're unique. They're different. They're not that super high beam like I've said, but it is a pretty palette and I'm glad I got it. I think that it's gorgeous. I do think that this is on sale at a couple different places. So if you're going to put in an order at Ulta and you didn't, you wanted to get this on sale, I'll try to link the places where it might be on sale. I think on Tarte's website it's definitely on sale. So you know that.  I have a whole bunch of stuff that I'm going to talk to you about from Macy's, but this right here has been so much fun. I already opened all of this and in a second I'll pull it all out and I'll show you, but it's got 25 different cubbies in it. What is really cool about it is it's half off right now. And then if you pull open this cubby right here, I can't pull it out without probably ripping it. It's got a $10 off coupon on your next purchase. So you're going to be able to get this home for I think $39.95 is what it is. Well, I shouldn't say that. It's $49.95 and then you get a $10 off your next purchase. So it's really gifting you back after you purchase it. So it's half off.  Here's the first things on one third of the calendar. So you get a mini size of the Lancome Tint Idol Mascara. That one is awesome. This is one of my favorites. It's such a good mascara. You also get a mini size of the Big Ego Tarte Mascara. That's one of their new ones. You get a travel size of the Coors Foaming Cream Cleanser. In my hand is Peter Thomas Roth Water Drench Broad Spectrum SPF 45 Moisturizer. You get an Elizabeth Arden Line Erasing Eye Cream with Ceramides. You get a Paracone MD. I always want to say Dr. Paracone. Paracone MD. Hypotency Classics Face Finishing and Firming Moisturizer. I'm getting very tongue-tied. Kota Lee. This one is the Radiant Serum Complexion Correcting. And you get a mini size of the Carolina Herrera Good Girl. I'm actually going to put this in a giveaway because I have two already. I love this fragrance. It is so feminine and so lovely. It's one of my favorite things ever. So that's going to go in a giveaway, not today, but I will be doing a giveaway very, very soon. And here is the middle third of it. And you get a Mario Badescu Two Ounce Facial Spray with Allo Herbs and Rosewater. You get, this is a Vince Camuto. I think that's how you say his last name. Illuminaire Roller Ball. This is a fragrance too. Actually, it's not a roller ball, but it's a little spray right there. It's a nice, really soft fragrance. I like that one. And then from Belief, Believe in Truth. This is the True Cream Aqua Bomb. Most of this stuff I haven't tried. So I'm excited to try it because I never have before. This is a little bitty sprayer of Max Fix Plus. I'm so glad to have that to travel with. It's going to make everything. And that is kind of why I wanted this too. How much fun to travel with all of this stuff. Oh my gosh, I used to use this all the time. Kiehl's Creme Decor. This is one of the best moisturizers for your body even. I used to use the heck out of this on my body a while ago. I've just forgotten about it. Eve Loam. This is one of her cleansers and she also gave you a cleansing cloth with that. So that's awesome. And then from Youth House. This is the Royal Black Diamond Eye Patches. And then there is a Pumpkin Retinol Eye Cream from Tony Moly. From Dr. Brant. There's the Neck Sculpting Cream, a trial. I'm so happy to get these trial sizes to put in when I travel. And here is the last third of it. So again, it has that $10 off your next purchase card that's in there. There's the Sunday Riley Luna. This is their Night Oil, a trial size of that. This is a travel size of the Urban Decay 24-7 Glide-On Pencil in their Black Color Zero. And then there's Estee Lauder Advanced Night Repair. That is a travel size of not travel trial size of that one. Two in there. And then there is a Bare Minerals Trial Size of their Veil. Their Setting Veil. They're really finely milled powder. That is a cult classic. Cashbox Always On Lipstick Liquid Lipstick. Sorry. This is a color that is really just kind of a unmuted, neutral rose color. And I thought I would try that one, even though I'm not a big liquid lipstick person. This is a Hair Serum from SB2. Never heard of this. Rejuvenating Hair Serum. Excited to try that. And then in it's Super Hero Mini Size of the Mascara. Okay, you guys, look at my little bin. It's totally full. This is everything that you're getting in this calendar. Here it is. It's all broken apart. It's all empty. But I still think that this is a good value for what you get. And then you get that $10 coupon as well. So I've thrown a ton of stuff at you today. I hope that there were some good ideas in here for you. I want to say thank you so much for everybody that's been using my links. It does help my channel and does help to replenish what I can do for you guys. I'm really excited about this advent calendar. I'm super excited about the sale at Ulta. I'm going to head over and make my order right now. The shirt I can link. It's got some cool, you know, cold shoulder little vibe going on right here. I'm pretty sure I can link it. I'm pretty sure. And my earrings, if I can find them, I will link them. I actually got these at Fred Meyer. If anybody has a Fred Meyer around you so that you know. Love you guys so very much. Please take care of yourselves. I hope everybody is doing well. I will see you again very soon in my next video. I hope. Bye friends!


Hi again Red Hat Developers, this is Jason with the Red Hat Developers program. I'm here with Charlotte M. Ellett and she's going to show us how to quickly deploy a .NET app on OpenShift. So I'm Charlotte M. Ellett. I'm a game developer working on the OpenShift team at Red Hat, working on .NET projects. Today, I want to talk about some really quick tips for getting your ASP.NET application up on OpenShift. This is a subject that I've covered in an ongoing series of blog posts that are up on the OpenShift blog currently, including a tutorial going into how to make a really simple app in Visual Studio 2015 and get it up on OpenShift Online. You can find these blogs and other amazing projects and news for my teammates at blog.openshift.com. You also may want to sign up for OpenShift Online account at OpenShift.com if you'd like to try everything out the quick way about having to install anything on your machine, or you can also find downloads at OpenShift.org if you want to experiment locally on your own machine instead. All that you should need in either case is a GitHub account. So again, here are the three most important things that you must do with your ASP.NET app. There's some code that you must add to get your app working on OpenShift. So I show this in more depth in my tutorials, but I will go over it briefly here in this talk. You will have to change the port from the default that Visual Studio picks to 8080 in your project. So you have to be listening to 48080. When using an S2I or Source2Image in your OpenShift project, keep in mind that all images are not built the same. Just because it says it's a .NET image doesn't mean it will work for your app. If your S2I is failing, I recommend looking for one from an official source or one that others have recommended because they had success with it. For using .NET Core 1.0 and 1.1 in OpenShift, I recommend looking up the S2I .NET Core from Red Hat-Developer on GitHub. So if you put up your app and at first it seems like it's not working, it may not necessarily be your app, it may be an issue with the S2I. Finally, make sure that you're using the correct version of .NET Core. You need 1.0 for apps developed in 2015 editions of Visual Studio and .NET Core 1.1 for 2017. For my tutorial project that's up on the OpenShift blog, I made a quick little app that allows you to create and name a horde of some text-based cats and tell them what to say. You can get a list of your cats and view the sound that they make by going to the URL that's created for them. This is a really fast little project that goes over some of the fundamentals and will have you completing your first ASP .NET project in a very short time depending upon your skills in C-Sharp. And you can have something up on OpenShift in just a few more minutes after that. However, you need to make a few changes to your code to get it ready. So I have some code snippets that were taken from my tutorial that I've highlighted here to help point out. There's really only a few lines that you need to add. So I created my project with templates in Visual Studio Community 2015. I selected this based on its popularity. So that's where my code snippets are taken from and it's the program .cs file that's created with my modifications to it. So you can see on the first one, we make sure that we're using the Microsoft.extensions.configuration. The second change is you want to have configuration builder and add environment variables. It's hard to explain, but you can see it in the slide there. This one is important for making sure that you're listening to port 8080. That will be needed for OpenShift and when you first create your project in Visual Studio, it selects a port for you that I don't know what it's based on, but it has some interesting selections. They're not 8080. This is the final step. Make sure you have UZRLs, parentheses URL in there. Now your ASP.NET app should be configured to listen to port 8080. Next when putting your app on GitHub, make sure that the base directory of your Git repo is the one that contains your project.json file. OpenShift will need to be able to find this, otherwise it's going to tell you that that file does not exist. It can't build and so on. That's important to make sure your file structure has that on the base of your repo. Now you should be ready to create your project on OpenShift. Next you'll be telling it which S2I that you want to use. Again, I recommend checking for a release from Red Hat-Developer-GitHub account or something else that is officially recommended or that others have had success with. If everything has gone correctly so far, you should now be able to navigate to Add to Project if you're looking at OpenShift to the web console view. And you should see .NET as an option in the Languages menu. Again, choose the .NET Core 1.0 if you have 2015 projects or 1.1 for 2017. So make sure that you're using the correct version of .NET Core or your app is not going to build. Now everything should be building and deploying automatically. It'll be up and running soon. It's that simple. This process lets you quickly put your .NET app out there on the web. That's one of the things I like about OpenShift online. And you can take advantage of all the features that it has as a container platform as well. You can scale up the number of pods, scale them down, implement health checks, metrics, quotas, and more. You have the option of using a web console interface or CLI. And the web interface, you can even easily open a terminal into your pod and poke around in there to see how your app is working. Like I did in the screenshot here with my Cat Horde app. Just to quickly do C-U-R-L, make sure that everything's working in there. That's it, really quick, easy tips for getting up your .NET app up on OpenShift. And thank you for me and the rest of the OpenShift team.


Party time, Jaspie's Jersey Fest is sold out. Time to party. So we sold out all the breaks that we needed to do for the Jersey Fest. It's a great lineup here, Jersey Fest. Big thanks to everyone who tried to get tickets here. Not everyone is gonna get tickets in Jersey Fest, but I appreciate everyone who tried. Now we've been keeping track of that list on our schedule page here. And here are the party people that got their passes to Jersey Fest. So thanks, everybody. There's the break right next to there. So we had to fill up 20, because there's 20 jerseys that were gaming away. The last one, the most recent one's even K with that getting to that top's Chrome Black Star Wars break. Winning another spot. We won a spot earlier than that three and two baseball break. All right. So there's all the names right here in one list. And we'll use one dice roll for both lists. And here's the list of the autographed jerseys. And we're randomizing names and jerseys. And we're matching you up with something. So good luck. Let's roll it. Randomize it one and a five. Six times for each list. Good luck, everybody. One, two, three, four, five. And once more, sixth and final time. We got Ed down to David. One and a five, six times for the jerseys. One, two, three, four, five, and six. So we got Jack Eichel down to Emmett Smith. All of these are nice jerseys.  So we got Jack Eichel down to Emmett Smith after six. So here's how it shakes out for everybody. And congrats, everyone gets something. Ed with the Jack Eichel. Rob with the SGA, Shay Gildes Alexander. He's been hot. Reese with Joe Montana, nice Chad with Dennis Rodman and Nick Chubb. Ivan with Gary Payton. Kevin with Vinicius Jr., great soccer player there. William Jalen Suggs, nice. Stephen K, Steve Young. David, DK Metcalf, Chris Larry Bird, Matthew Lionel Messi. Ed with the Garrett Wilson. Dustin, John Elway. Jeffrey, Jalen Waddle. Stephen K, Julia Serving. Matthew, Erling Holland. Chad with CD-Lam. Brian with Ronaldinho. And David B with the Emmett Smith. Congrats, all great players here. Either Hall of Famers, superstars, rising stars. Big thanks to everybody who got into all of the action. I'll give you an example. I don't know if we're sending the actual boxes, but I wanted to show you just an example of what some of these jerseys look like. So oh, this is the Gary Payton. So all of these will have their own little tag right here. And this one is actually, who's this one going? Ivan with the Gary Payton. So you got all the retail tags right there at the Mitchell and Ness, nice. So you get all the tags right there. You can already tell by the quality just by holding the jersey. You can, Gary Payton's ownership group might bring the SuperSonics back to Seattle. All right, so then you've got the autograph and of course the phonetics official sticker right there as well.  Thanks for watching. Thanks for breaking with us. I'm Joe for jaspyscasebrakes.com and I'll see you next time for the next promo. Bye-bye.


who doesn't know what anime is. Okay, I think everyone knows. Basically, anime is the Japanese version of Cartoon. Yeah, so, and you know, this is a huge fan base of a lot of shows that we love to watch the anime and we also love to collect stuff. We also love to go to cinemas to watch the movies. But you know, there are a lot of things happening around the world and it's too hard to track all of them. Especially like, there can be a couple hundred news of a single character coming out every day. So what I'm trying to do is to provide you this platform, provide us this platform that we can easily passively receive updates on the things that we are interested in. So, like, here's a demo. So for example, I'm interested in a couple of characters like, namely, this girl. So it's... Well, yeah, so this is... So I'm going to spend some editing. So this girl has a new, we call it a figure, which is a kind of plastic toy. And coming up, so I don't want to miss it because all these things go by pre-order. If you don't pre-order it, it's gone and they will never be produced again unless at the mercy of the producer that they decide to, maybe in 10 years they produce another batch. So you can, if you're interested, it can expand to see more beautiful images. Then there are other types of events, like movie. So this is a movie that was just shown in Singapore like since 30th November. And the tickets are really limited. So if you miss it, it's really hard to catch it. So buy ticket now if you're interested. And yeah, similarly... Oh, sorry. And you can watch the trailer if you're interested or there's a new game coming out of it. So the important thing is that if you notice the left-hand corner is that these are all go-by characters. So because if you watch anime, you'll know that you love just a couple of them. You don't love all of them. I will just show the things that your favorite characters are in instead of everything else. So if you go to DeviantArt to search by some shows, you see just everything and good or bad, mostly bad stuff. So it will be a very curated, nice list of stuff that you're interested in. So that's it. So what's your favorite anime? Hard to say. Fate, like that one, Fate's Day and Night. But I'm really into Love, Love and Down. Other things? Any other questions from anyone? Yeah. Okay, go for it. What would be the bone-out factor in this? Because this seems very... Yeah, you're just... It looks legit. Really? I mean, it depends on the population, right? What percentage of people that here are really into this kind of thing? The fewer the people, the more polyothesis. Everybody here likes to... Secretly read. Secretly read? And then vote for us. Also pricing structure. Oh, pricing structure. Yeah, yeah, sure. It's go by a subscription. So you pay every month. So if you don't pay, it's okay. You can use it for free, but you can only follow 10 characters. But I guess 10 is not enough, right? Really? Who was an avid strategy? No. We don't have a huge... We don't want to be bought, but this can be huge, you know? So the ultimate goal is that you don't need to go anywhere else. Not even Facebook for...  Any other questions? So how are you doing the character-specific scraping? I'm just curious about that. Because the characters all have their own names. But in some cases, there will be like an image that, you know, maybe... Are you doing image-based stuff? Because, you know, some of the characters... They might not have it on the caption. It might not be in the accompanying article, but it's related to that character and that constellation of characters. Oh, this is so serious. But, you know, I do have this thought of. So at the beginning, this is all curated stuff, right? From DeviantArt, it's from Pixiv, it's from my anime list. When we scrape them, it's hard to make it correct 100% of times. But in the future, they won't exist. This is the only one left. So the publishers will come here, the fans will come here, and there will be official stuff here.  So, yeah. Any other comments? How are you going to give people the two, to build communities and bring the one together? So it's like we both... Yeah, this is really a community for anime goers. Any other questions, comments? Alright, thank you very much. Thank you.


Alright today's question guys comes from a buddy Jake and he says I've had a lucid dream But it seems to just last two seconds and it just stops, right? It's very short. I tend to enter a lucid dream and be like, okay. Yes. I'm dreaming. It's happened It's worked but then what happens is he just wakes up and he says why do I wake up? Why do why do the lucid dreams last so little time? Why do they just seem like a flash in a pan, right? Well, this is something which lots of people lots of people have the same problem Same problem where they learn how to lose a dream. They learn basic techniques for controlling your dreams Basic techniques, you know the way can juice the wild meditation and They have a lucid dream right and maybe you're you're similar. Maybe you've had the same sorts of issues I don't know leave a comment and what happens is you enter a lucid dream and straight away you wake up and This can happen for a number of reasons.     Okay The more you shake it up so the more you run around having sex with people or tearing down buildings or Getting into danger or perceived danger Just less stable the organism's gonna be right and another thing is if you for example run around saying I'm lucid I'm dreaming here. Here. I am.  It might not happen straight away It might not even happen every time But generally speaking And I don't know why it works, but it does Generally speaking the more you shake things up in that dream world the less stable it's gonna be and so the first thing to do If you really want to stay in the dream for longer at least until you're more experienced, right? Because the more experienced you get the more skills you have for staying in the dream stabilizing it that sort of thing If you're less experienced just try and do less engaging or exciting things I know it sucks and I know it's not what you want to hear but until you've learned how to stabilize and stay in the dream for longer The most important thing you need to do is just to be less engaged with what you're doing Don't go around shouting.  I mean it's still cool, right? You still had to lose a dream And well done for that. That's that's an achievement in itself, but in order to have longer and more profound experiences you need to stabilize the dream and at the start at least right the first few months of your practice You're gonna have to do it the I guess you can say the boring way right the the way where you're not as engaged and You're not doing those crazy emotionally Emotionally arousing things Okay, so that's the first one. I'm not sure if this applies to you, but then I'm just going on message. I received the email received the second one okay, and this this comes down to the I guess I want to say the physics of the dream even though it's not really the right term I mean the sort of foundation the structure and the the basic things you would have had to do to Have a lucid dream and to enter the dream space. So What I mean by that is If you are not getting enough sleep if you're tired, right? No, sorry if you're not tired and you're not getting enough sleep The dream won't be as stable So a really effective way of making the dream a lot more stable and staying in it for longer and having more lucid dreams just comes down to exercising And like recently I've been going to the gym a lot more often And I find that just by doing that just nothing else like just that alone Makes my dreams feel like they're lasting longer It makes them more vivid and it makes them more likely to be lucid. I've had two lucid dreams in the last few days right just naturally because I've been exercising more and So that's another thing you could try you want to make yourself tired Uh, so that when you go to sleep the sleep that you have is really stable And it's almost like you're sedating yourself, right?