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Joseph 0 , Hlrschfelder c c bY JOSEPH 0, HLRSCHFELDER University of Wisconsin Theoretical Chemistry Institute Hadison, Wisconsin Peter Debye Award Speech at American Chemical Society Meeting, Pittsburgh, March 28, 1966 * This research was supported by the following grant: National Aeronautics and Space Administration NsG-275-62. I am thrilled that this award should carry the name of the great Peter Debye. The name, DEBYE, brings to mind a large number of brilliant achievements in electromagnetic theory, the scattering I of light, the behaviour of strong electrolytes, the stability of coiioidai suspensions, and tha farces betyeen biological mlecules, His work is always thorough and his ideas are always clear and profound. Besides being a wonderful scientist, Debye is a wonderfully nice person and a great teacher. His tremendous enthusiasm has been a source of inspiration to three generations of scientists. On occasions like this, one feels very humble and inadequate. I am in no sense brilliant, just a hard working guy with a great deal of tenacity. Whatever success I have had stems from the help which I have received from a great many wonderful people. Indeed, I am impressed with the deep debt of gratitude which I owe to my family, my friends, my colleagues, my teachers, and my students. It is upon their shoulders that I have tried to build. Dick Bernstein told me that I should make this a very personal speech. Thus, I will take the occasion to do a bit of philosophizing. Let us start with some of the words of wisdom that have meant a great deal to me. I owe a great debt to Henry Eyring for having given me a start on my scientific career. The Eyring philosophy I best remember is: 1 HENRY EYRING "BE NICE TO THE GUYS ON THE WAY UP so THAT THEY WILL BE NICE TO YOU ON THE WAY DOWN". In nature, or complicated systems, there is usually only ONE slow step or bottleneck which determines its behaviour. Always ask yourself, how might the phenomena occur. Make a GEDENKS-model. It will suggest the proper groupings of variables - a big help in semi-empiricizing. "A SCIENTIST'S ACCOMPLISHMENTS ARE EQUAL TO THE INTEGRAL OF HIS ABILITY INTEGRATED OVER THE HOURS OF HIS EFFORT". To Eyring, every problem in nature can be studied theoretically. The first step is to ask yourself what mipht the solution look like. 1 I think that Einstein had much the same viewpoint: 1. I learned a great deal abmt Einstein from his research assistant, Nathan Rosen. Rosen collaborated with me in our calculations of the energy of H3 and H3+. He showed me that by properly systematizing the procedure and the format, I could reduce my computational effort by a factor of ten. 3 A'iSET E I3STE IN "IT IS EASY, JUST HARD TO DO!" Einstein seldom sought direct solutions to his equations. His first question was, "under what other conditions could these equations arise?" He learned a great deal from the way in which other people had solved these equations in other types of problems. "NATURE IS SIMPLE, IT IS WE WHO ARE COMPLICATED!" Surely it pays to spend a considerable amount of time looking at your problem from all different directions. Think before you leap! In this case, leaping corresponds to committing yourself to a particular research technique. My first research as a graduate student was under the direction of Edward Condon. From him I learned that a theoretician should have a broad background. EDWARD U. CONDON A theoretician'should be well-versed in a wide range of experimental techniques and facts. The three functions of a theoretician are : 1). Suggest new types of experiments. 2). Suggest new interpretations of existing data. 3). Further develop the theory so that it may become a more powerful tool in the understanding of nature. 4 At the Bikini Atom Bomb Tests in 1946, my title was Chief Phenomenologist. John Magee and I had the job of predicting all of the different effects of the bomb SO that the experiments could be properly set up. Enrico Fermi felt very strongly that every scientist should be trained as a phenomenologist. He trained his students to get order of magnitude solutions to arbitrary questions. A typical Fermi question was "Estimate the number of railroad locomotives in the United States". It is interesting to note Fiat Chemical Engineers are regarded as the most flexible and possessing the best background for Operational Research Analysis , where such ability is required. I was, indeed, fortunate to be a graduate student at Princeton during the First Golden Ape of Quantum Chemistry, 1931-6. This was a wonderful period of great discoveries and Princeton was the hub. It was a period during which many people had high hopes of explaining all of the physical and chemical properties of material and, indeed, all of natural phenomena in terms of the basic laws of physics. Even such erudite physicists as Dirac, Van Vleck, and London concocted simple approximation procedures which they hoped would help to explain molecular structure. It was a period of high hopes in which theoreticians took a fresh look at all sorts of natural phenomena and guessed at their mechanism. The methods which were used in those days were crude compared to our present techniques, but the men who used them were not afraid to stick their necks c out. Of cwrse3 the theoretical predictions served 8s challenges to the experimental scientists ad were especially valuable when the theory suggested a critical experiment. Thus a very stimulating rivalry developed between the experimental and the theoretical men. The result was an era of exciting discoveries. In a nutshell, the message which I want to convey today is that for the last 30 years theoretical chemists have been preoccupied with developing their mathematical techniques - that is, developing molecular quantum mechanics and statistical mechanics on a firm ab-initio basis resulting from accepted laws of physics. The importance of this theoretical development cannot be overemphasized. With the advent of giant high speed computing machines, new types of mathematical methods, and the renewed help of the theoretical physicists it appears that within five to ten years we will be able to make accurate theoretical predictions of loost of the physical and chemical properties of matter. Then there will be a change of emphasis. The theoretical chemists must start preparing themselves and their students ripht now for this change of emphasis. At present, theoretical chemists are concentrating on high power mathematics. They are also concentrating on very specific problems and only using a narrow range of techniques. The emphasis will shift from developing new methods to applying existing methods. Then the theoretical chemists must have a broad knowledge of experimental ? 6- physics ar,d experimental chenistry as well as a broad knowledge of theoretica 1 chemi s try .zid theore t Ec2 1 phys ics. In the development of basic ab-initj-o spproaches to molecular quantum mechanics and statistical mechanics rigor Ls ti virtue a3d absolutely essential in order to establish definitive results. But in the applications of theory to the world around us, the theory is most useful when it is stretched beyond those things which we know for sure. Thus, it will be important that the theoreticians of the future -not be afraid to stick their necks out and make 11guestimates" which can serve to guide experiments. During the period 1931-6, thanks ta the genius of Linus Pauling and Henry Eyring, theoretical chemists ,d&l try to apply their meager theoretical knowledge as far as they could stretch it. Out of this came many exciting discoveries. I predict that the period 1970-80 will resemble this first golden age of quantum chemistry. Therefore I will tell you a little bit about the good old days. In 1931 quantum mechanlcs, in its present form, was only a few years old. No one knew its limitations and important discoveries were made every few months. Quantum mechanics was first applied to problems of atomic energy. The explanation of the relative spacings or the "flags" corresponding to the splittir,g of multiplets was one of the first b triumphs. The determilation of the absolute values of the splittings required the evaluation of a set of radial integrals. 7 Ed Condon set a number of us young graduilte atiidents to wak on these integrals, which subsequently became a part of Condon and %or t iey ' s f arnous treatise . Of course, modern quantum mechanics was designed to give the correct energy levels for atomic hydrogen. It was Egil Hylleraas who shed that it also worked for the two-electron helium atom. At one time or other, Hylleraas used or developed almost every basic technique which we use in quantum mechanics: different types of per turba t ion and var iat iona 1 pr incip le s , corre lated or bita 1s , configurational interaction, etc. All of Hylleraas' calculations were made on a hand-cranked desk calculating machine. The next generation of quantum mechanicians had electric power to turn the crank. The early treatment of many-electron atoms was very crude. Hartree expressed the wave function for an atom as the product of one-electron orbitals. These orbitals were supposed to be the solutions to a set of coupled differential equations which seemed hopelessly difficult to solve. Eventually Hartree was able to obtain approximate solutions on a mechanical differential analyzer which he built out of Mechano parts (You may remember having a Mechano toy when you were a child). 2 The early differential analyzers were very interesting. Vannevar Bush' first model was completely electrical using a house-type watt- ----- 2.
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