The Nobel Prize in Chemistry 1992
Rudolph A. Marcus
Rudolph A. Marcus
Born: 21 July 1923, Montreal, Canada
Affiliation at the time of the award: California Institute of Technology (Caltech), Pasadena, CA, USA
Prize motivation: "for his contributions to the theory of electron transfer reactions in chemical systems"
Field: Theoretical chemistry
My first encounters with McGill University
came when I was still in a baby carriage. My mother used to wheel
me about the campus when we lived in that neighborhood and, as
she recounted years later, she would tell me that I would go to
McGill. There was some precedent for my going there, since two of
my father's brothers received their M.D.'s at McGill.
I have always loved going to school. Since neither of my parents had a higher education, my academic "idols" were these two paternal uncles and one of their uncles, my great-uncle, Henrik Steen (né Markus). My admiration for him, living in faraway Sweden, was not because of a teol.dr. (which he received from the University of Uppsala in 1915) nor because of the many books he wrote - I knew nothing of that - but rather because he was reputed to speak 13 languages. I learned decades later that the number was only 9! Growing up, mostly in Montreal, I was an only child of loving parents. I admired my father's athletic prowess - he excelled in several sports - and my mother's expressive singing and piano playing.
My interest in the sciences started with mathematics in the very beginning, and later with chemistry in early high school and the proverbial home chemistry set. My education at Baron Byng High School was excellent, with dedicated masters (boys and girls were separate). I spent the next years at McGill University, for both undergraduate and, as was the custom of the time, graduate study. Our graduate supervisor, Carl A. Winkler, specialized in rates of chemical reactions. He himself had received his Ph.D. as a student of Cyril Hinshelwood at Oxford. Hinshelwood was later the recipient of the Nobel Prize for his work on chemical kinetics. Winkler brought to his laboratory an enthusiastic joyousness in research and was much loved by his students.
During my McGill years, I took a number of math courses, more than other students in chemistry. Upon receiving a Ph.D. from McGill University in 1946, I joined the new post-doctoral program at the National Research Council of Canada in Ottawa. This program at NRC later became famous, but at the time it was still in its infancy and our titles were Junior Research Officers. The photochemistry group was headed by E.W.R. Steacie, an international figure in the study of free-radical reactions and a major force in the development of the basic research program at NRC. I benefitted from the quality of his research on gas phase reaction rates. Like my research on chemical reaction rates in solution at McGill (kinetics of nitration), it was experimental in nature. There were no theoretical chemists in Canada at the time, and as students I don't think we ever considered how or where theories were conceived.
About 1948 a fellow post-doctoral at NRC, Walter Trost, and I formed a two-man seminar to study theoretical papers related to our experimental work. This adventure led me to explore the possibility of going on a second post-doctoral, but in theoretical work, which seemed like a radical step at the time. I had a tendency to break the glass vacuum apparatus, due to a still present impetuous haste, with time-consuming consequences. Nevertheless, the realization that breaking a pencil point would have far less disastrous consequences played little or no role, I believe, in this decision to explore theory!
I applied in 1948 to six well-known theoreticians in the U.S. for a postdoctoral research fellowship. The possibility that one of them might take on an untested applicant, an applicant hardly qualified for theoretical research, was probably too much to hope for. Oscar K. Rice at the University of North Carolina alone responded favorably, subject to the success of an application he would make to the Office of Naval Research for this purpose. It was, and in February 1949 I took the train south, heading for the University of North Carolina in Chapel Hill. I was impressed on arrival there by the red clay, the sandy walks, and the graciousness of the people.
After that, I never looked back. Being exposed to theory, stimulated by a basic love of concepts and mathematics, was a marvelous experience. During the first three months I read everything I could lay my hands on regarding reaction rate theory, including Marcelin's classic 1915 theory which came within one small step of the Transition State Theory of 1935. I read numerous theoretical papers in German, a primary language for the "chemical dynamics" field in the 1920s and 1930s, attended my first formal course in quantum mechanics, given by Nathan Rosen in the Physics Department, and was guided by Oscar in a two-man weekly seminar in which I described a paper I had read and he pointed out assumptions in it that I had overlooked. My life as a working theorist began three months after this preliminary study and background reading, when Oscar gently nudged me toward working on a particular problem.
Fortunately for me, Oscar's gamble paid off. Some three months later, I had formulated a particular case of what was later entitled by B. Seymour Rabinovitch, RRKM theory ("Rice-Ramsperger-Kassel-Marcus"). In it, I blended statistical ideas from the RRK theory of the 1920s with those of the transition state theory of the mid-1930s. The work was published in 1951. In 1952 I wrote the generalization of it for other reactions. In addition, six months after arrival in Chapel Hill, I was also blessed by marriage to Laura Hearne, an attractive graduate student in sociology at UNC. She is here with me at this ceremony. Our three sons, Alan, Kenneth and Raymond, and two daughters-in-law are also present today.
In 1951, I attempted to secure a faculty position. This effort met with little success (35 letters did not yield 35 no's, since not everyone replied!). Very fortunately, that spring I met Dean Raymond Kirk of the Polytechnic Institute of Brooklyn at an American Chemical Society meeting in Cleveland, which I was attending primarily to seek a faculty position. This meeting with Dean Kirk, so vital for my subsequent career, was arranged by Seymour Yolles, a graduate student at UNC in a course I taught during Rice's illness. Seymour had been a student at Brooklyn Poly and learned, upon accidentally encountering Dr. Kirk, that Kirk was seeking new faculty. After a subsequent interview at Brooklyn Poly, I was hired, and life as a fully independent researcher began.
I undertook an experimental research program on both gas phase and solution reaction rates, wrote the 1952 RRKM papers, and wondered what to do next in theoretical research. I felt at the time that it was pointless to continue with RRKM since few experimental data were available. Some of our experiments were intended to produce more.
After some minor pieces of theoretical study that I worked on, a student in my statistical mechanics class brought to my attention a problem in polyelectrolytes. Reading everything I could about electrostatics, I wrote two papers on that topic in 1954/55. This electrostatics background made me fully ready in 1955 to treat a problem I had just read about on electron transfers. I comment on this next period on electron transfer research in my Nobel Lecture. About 1960, it became clear that it was best for me to bring the experimental part of my research program to a close - there was too much to do on the theoretical aspects - and I began the process of winding down the experiments. I spent a year and a half during 1960-61 at the Courant Mathematical Institute at New York University, auditing many courses which were, in part, beyond me, but which were, nevertheless, highly instructive.
In 1964, I joined the faculty of the University of Illinois in Urbana-Champaign and I never undertook any further experiments there. At Illinois, my interests in electron transfer continued, together with interests in other aspects of reaction dynamics, including designing "natural collision coordinates", learning about action-angle variables, introducing the latter into molecular collisions, reaction dynamics, and later into semiclassical theories of collisions and of bound states, and spending much of my free time in the astronomy library learning more about classical mechanics, celestial mechanics, quasiperiodic motion, and chaos. I spent the academic year of 1975-76 in Europe, first as Visiting Professor at the University of Oxford and later as a Humboldt Awardee at the Technical University of Munich, where I was first exposed to the problem of electron transfer in photosynthesis.
In 1978, I accepted an offer from the California Institute of Technology to come there as the Arthur Amos Noyes Professor of Chemistry. My semiclassical interlude of 1970-80 was intellectually a very stimulating one, but it involved for me less interaction with experiments than had my earlier work on unimolecular reaction rates or on electron transfers. Accordingly, prompted by the extensive experimental work of my colleagues at Caltech in these fields of unimolecular reactions, intramolecular dynamics and of electron transfer processes, as well as by the rapidly growing experimental work in both broad areas world-wide, I turned once again to those particular topics and to the many new types of studies that were being made. Their scope and challenge continues to grow to this day in both fields. Life would be indeed easier if the experimentalists would only pause for a little while!
There was a time when I had wondered about how much time and energy had been lost doing experiments during most of my stay at Brooklyn Poly- experiments on gas phase reactions, flash photolysis, isotopic exchange electron transfer, bipolar electrolytes, nitration, and photoelectrochemistry, among others-and during all of my stay at NRC and at McGill. In retrospect, I realized that this experimental background heavily flavored my attitude and interests in theoretical research. In the latter I drew, in most but not all cases, upon experimental findings or puzzles for theoretical problems to study. The growth of experiments in these fields has served as a continually rejuvenating influence. This interaction of experiment and theory, each stimulating the other, has been and continues to be one of the joys of my experience.
Honors received for the theoretical work include the Irving Langmair and the Peter Debye Awards of the American Chemical Society (1978, 1988), the Willard Gibbs, Theodore William Richards, and Pauling Medals, and the Remsen and Edgar Fahs Smith Awards, from various sections of the ACS, (1988, 1990, 1991, 1991, 1991), the Robinson and the Centenary Medals of the Faraday Division of the Royal Society of Chemistry (1982, 1988), Columbia University's Chandler Medal (1983) and Ohio State's William Lloyd Evans Award (1990), a Professorial Fellowship at University College, Oxford (1975 to 1976) and a Visiting Professorship in Theoretical Chemistry at Oxford during that period, the Wolf Prize in Chemistry (1985), the National Medal of Science (1989), the Hirschfelder Prize in Chemistry (1993), election to the National Academy of Sciences (1970), the American Academy of Arts and Sciences (1973), the American Philosophical Society (1990), honorary membership in the Royal Society of Chemistry (1991), and foreign membership in the Royal Society (London) (1987) and in the Royal Society of Canada (1993). Honorary degrees were conferred by the University of Chicago and by Goteborg, Polytechnic, McGill, and Queen's Universities and by the University of New Brunswick (1983, 1986, 1987, 1988, 1993, 1993). A commemorative issue of the Journal of Physical Chemistry was published in 1986.
From Les Prix Nobel. The Nobel Prizes 1992, Editor Tore Frängsmyr, [Nobel Foundation], Stockholm, 1993
This autobiography/biography was written at the time of the award and later published in the book series Les Prix Nobel/Nobel Lectures. The information is sometimes updated with an addendum submitted by the Laureate.
Copyright © The Nobel Foundation 1992
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