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Biographical Memoirs Volume 66 (1995) / Chapter Skim
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Frederick Kaufman
Pages 206-225

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From page 207...
... Many of these studies were made possible by Kaufman's pioneering work in the 1950s, which adapted the venerable discharge-flow technique of Wood and Bonhoeffer into a modern too] for gaining information on the rates and products of elementary reactions, the simple building blocks of complex reaction mechanisms.
From page 208...
... Although also engaged in pyrolysis and other high-temperature combustion studies, his interest in exploring the underlying elementary gas-phase reactions increased during the early 1950s. With the award of a Rockefeller Public Service Award in 1955, he was able to spend a year in the Department of Physical Chemistry at Cambridge University, which Professor Norrish had established as a center for kinetics studies.
From page 209...
... to promote studies in the natural and social sciences, engineering, and health areas concerned with the aerospace field. Several prominent scientists were immediately attracted to the SRCC, including Thomas Donahue, an aeronomer and the first director of the SRCC, who was already on the faculty of the Pitt Physics Department, and the physicists Wade Fite, Manfred Biondi (moving across town from the Westinghouse Corporation)
From page 210...
... He was also fully involved in the teaching program at Pitt, having a preference for the general chemistry courses, while his advanced graduate course in chemical kinetics, presented every second year, provided an excellent introduction to the theory and practice of that field for a succession of physics and chemistry graduate students and postdoctoral fellows. He won Outstanding Educator of America awards in 1971 and 1975.
From page 211...
... Initially at the Ballistic Research Laboratories and then at Cambridge University in 1955-56, he characterized gas phase titration reactions of N and O atoms, in particular that of oxygen atoms with nitrogen dioxide, and monitored their progress by chemiluminescence (i.e., ultra-violet and visible light emitted during the reactions)
From page 212...
... This detection technique evolved during the next decade to the more sensitive resonance fluorescence, in which the fluorescence following the photon absorption event was monitored, and then to laser-excited fluorescence, in which the resonance lamp was replaced by a much more intense tunable laser light source. With these improvements a powerful technique was in place to allow a vast range of elementary reactions to be studied.
From page 213...
... Initial rate investigations were indirect and produced widely scattered values of the rate constant. In his first publication on this reaction, in 1978, Kaufman carefully discussed the criteria for successful modeling of the reaction system and was characteristically cautious about the validity of the derived rate constant.
From page 214...
... His contributions were recognized by the dedication of the massive 1985 atmospheric ozone report to his memory. His special role in the chemical kinetics community was likewise recognized with the posthumous award in 1987 of the Polanyi Medal by the gas kinetics group of the Royal Society of Chemistry.
From page 215...
... Collaboration with his SRCC colleagues, especially Wade Fite and Fred Biondi, helped to spur his involvement in two related areas of reaction rate measurements, namely ion-molecule reactions and reactions of electronically excited species. In the first of these areas, his group undertook a major study of reactions of ions with water and of water ions, H2O+, with several neutral molecules.
From page 216...
... no signal except for possible weak resonance fluorescence; however, on the following orbit with the craft now 500 meters apart, excellent absorption and fluorescence data were obtained. How did Fred Kaufman conduct his research?
From page 217...
... First, he established the mechanism of combination of oxygen atoms and nitric oxide into these states, discovering the intricate competition between radiation by these states and their collisional deactivation to lower energy, non-emitting states. Beginning in 1966 his group populated the same states by exciting nitrogen dioxide with visible light, later using the temporal development of the fluorescence to gain analogous information but in more detail.
From page 218...
... Although he referred in print to his nontheorist mind, he was keenly aware of the status of theory regarding thermal reaction rates. His graduate course on chemical kinetics was dominated by description and critical discussion of theories of bimolecular and unimolecular reactions.
From page 219...
... My reason for calling this meeting was the need to take stock of the present state of the field of elementary gas reaction kinetics: to assess the accuracy of measurement techniques; to discuss the compilation and evaluation of rate data; and, most importantly, to examine the predictive power of theory. The stock-taking was stimulated by recent advances in the direct experimental measurement of elementary atom or radical reaction kinetics and by the preoccupation of theorists with problems of detailed state-to-state dynamics at a time when the demand for rate constants, measured, calculated or guessed, is growing rapidly in such diverse fields as atmospheric chemistry, combustion, and pollution.
From page 220...
... and what detail is required (in a cost-benefit analysis sense) ; classical trajectory calculations; quantum corrections based on one-, two-, and three-dimensional theory; nonequilibrium effects in two-body reactions; energy transfer in dissociation/recombination reactions and its dependence on excitation energy, molecular complexity, and temperature; prediction of rate parameters over large temperature ranges for widely different molecular complexity or for series of reactants differing only in substituent effects; implication of energy disposal information for thermal rate constants; critical test cases presently available or to be developed for theory-experiment comparison.
From page 221...
... , routine three-dimensional classical trajectory calculations on many systems, ah initio and semiempirical potential energy surfaces, testing of various approximate theories against exact calculations in the easily accessible one-dimensional format (mainly for A + BC reactions) , development of improved statistical theories of dissociation-recombination reactions, and continued application of transition state theory, particularly in its thermochemical variant (Benson, Golden)
From page 222...
... There is clearly much more work to be done. What impresses me, however, is the general usefulness and resilience of simple transition state theory which, after early triumphs went into a lengthy eclipse only to reemerge as a surprisingly accurate (and sometimes as the only)
From page 223...
... 44:718-23. 1969 Elementary gas reactions.
From page 224...
... Detroit. 1979 Symposium on current status of kinetics of elementary gas reactions: predictive power of theory and accuracy of measurement: Introductory remarks.
From page 225...
... 87:570-74. 1983 Chemical kinetics and combustion: Intricate paths and simple steps.


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