© Copyright 1999 by the American Chemical Society
VOLUME 103, NUMBER 43, OCTOBER 28, 1999
John Kerry Thomas Biographical Sketch Prof. Kerry Thomas was born in 1934 in Llanelli, South Wales, an area of Wales between the mountains and sea, which is full of historic cites. J. Kerry Thomas learnt his love of boats and ancient history in this environment. Attended Llanelli Grammar School on a scholarship, where he learnt the joys of cricket and chemistry both from a stern but encouraging chemistry master, Mr. D. Roderick, who had actually carried out photochemical studies in his student days at the University of Wales. In 1951, he obtained a State Scholarship to Manchester University. This was a particularly exciting time at Manchester, when the physical chemistry department contained distinguished scientists such as M. Polanyi, M. G. Evans, M. Sqwarc, M. Kasha, N. Hush, and others. Again photochemistry appears as G. Porter spent a short time in the area and gave several seminars at the University which greatly influenced J. Kerry Thomas. After graduating in 1954, he stayed at Manchester to study for a Ph.D. under the renown kineticist Professor J. H. Baxendale.
Baxendale abounded in enthusiasm for research, and this just suited J. Kerry Thomas, learning the tricks of the trade, solutions of complex kinetic equations, photochemistry, radiation chemistry, and even glass blowing. His first research problem was on the UV radical degradation of polymethacrylic acid, which was suggested by Professor G. Gee, the head of the department, who thought that J. Kerry Thomas lacked the necessary enthusiasm for polymer chemistry. This was a fateful move as J. Kerry Thomas has continued to add to the physical chemistry of PMA to the present day. Musing on his role in polymer chemistry he sometimes calls himself a “reluctant” polymer chemist. He was fortunate to have the mercurial Professor J. Weiss (Haber & Weiss fame) for a Ph.D. examiner. He recalls that the Ph.D. examination was very exciting and more like a research seminar. The two remained friends for years after this early student-examiner meeting. The years at Manchester were particularly fruitful when J. Kerry Thomas became immersed
10.1021/jp991710y CCC: $18.00 © 1999 American Chemical Society Published on Web 09/21/1999
9056 J. Phys. Chem. B, Vol. 103, No. 43, 1999 in both photochemistry and radiation chemistry, a two pronged approach to problems that he has continued throughout his career. At this state, he was introduced to the concept of pulse radiolysis using the new Linac at Metrovickers at Trafford Park. This technique was one to fascinate him all his career. In these early days, he measured the yield of Fe3+ ions produced on pulse radiolysis at 13 ( 1 ions per 100 eV of energy absorbed. This was considered reasonable but not sufficiently close to the accepted value of 15.6 for low intensity γ-rays. Later, at Argonne, he was able to show that the value was 13.3, the lower value resulting from the high radical concentration produced in the pulses. He spent a fruitful year at the National Research Council in Ottawa as a postdoctoral fellow with two well-known polymer chemists, Stan Bywater and J. Worsfold. There he developed the use of the ferric-acetoin system as an initiator of polymerization. However, his first love of radiation effects drew him back to the British Atomic Energy, at Harwell and Wantage, where he developed radiation methods to surface graft conducting monomers on nonconducting polymers. He recalls this as a time of great cricket, and great discussion with Alistair Johnson and Arthur Salmon. At Wantage, the three British schools of radiation chemistry, Newcastle, Leeds, and Manchester have much to discuss. In 1960 he went to Argonne National Laboratory to work with the renown Edwin J. Hart. He recalls that there was “nothing that Ed couldn’t do experimentally”. He got back into pulsing with a vengeance and in conjunction with Hugo Fricke (of the Fricke Dosimeter fame) used the concept of the old highintensity yield of 13.3 to measure the first rate constant for H atom reactions. Fast pulsed methods seemed to be his forte, and he soon had developed ways to measure the OH radical, CH3 rates of reaction, and other radicals. He also joined Ed Hart and Max Matheson to measure the first rates of reaction of the hydrated electron. These early microsecond studies answered a lot of questions, but faster response was needed. As soon as nanosecond pulses became available at Argonne, John Hunt and J. Kerry Thomas developed the first nanosecond pulse radiolysis system, and within a year the method was applied to the nanosecond pulsed laser systems that were now becoming available. With several co-workers he used the fast response of this system to establish for the first time direct observation of spur reactions, geminate ion recombination, the relaxation time of electrons in low temperature glasses, and the spectra of excited states of molecules. The latter studies were quickly converted over to new laser pulsed studies, where two photon excitation to give excited states of benzene and two photon ionization were established in the late 1960s. These areas expanded really rapidly due to much of the early work of J. Kerry Thomas and co-workers at Argonne. He received the Research Award of the Radiation Research Society for this early work and an honorary Doctor from the University of Manchester.
In 1970, he moved to Notre Dame continuing his nanosecond pulse laser and pulse radiolysis studies. By the development and use of fast pulse conduction methods with the late G. Beck, they were able to measure the rates of reaction of quasi-free electrons in hydrocarbons, a study which lead to a flurry of activity in this area as the Stokes-Einstein relationship failed due to the quantum mechanical nature of e- in these systems. It was time to open the work in new directions, and J. Kerry Thomas decided to use his methods in micellar systems. He was indeed fortunate at this time to have great co-workers, such as M. Gra¨tzel, K. Kalyanasundaram, Mats Almgren, and Franz Greiser, to name but a few, who literally threw themselves into the work. The work had a two-fold direction, to use radiation methods to describe micelles and colloids, and also to use the colloidal system to control desired features of radiation induced events. The output was prodigious, and the technique of microprobing of a system with excited states was established. This included the use of quenching reactions to monitor surface changes on micelles, the use of fluorescence free structure to monitor microenvironment and the exit and entry rates of surfactants and guest molecules in colloids, the Poisson distribution to measure aggregation number, etc. For this work, he was awarded the ACS Award in Colloid and Surface Science. His fascination with fast pulsing led G. Beck and J. Kerry Thomas to develop a new picosecond emission and absorption system for pulse radiolysis using the fine structure of the Notre Dame Linac. This was perfected further by a long collaboration with G. Beck at the Hahn-Meitner in Berlin. The final phase was a picosecond conduction system, which measured the picosecond rates of capture of electrons by small water pools in hydrocarbons. For the last 10 years J. Kerry Thomas has moved his studies to other microsystems, but of a more permanent nature, namely high surface area and porous silica and γ-Al2O3, and zeolites. The fast probing method has given a wealth of information on these systems and, in particular, allowed observation of etrapping by Na+ clusters and small H2O and methanol pools in the zeolites. He again states how fortunate he has been with co-workers, K. Iu, X. Lui, G. Zhang, R. Krasnansky, K. Koike, S. Ruettin, R. Kavanagh, E. Ellison, and many others. He fondly recalls his several sabbatical visits in Berlin, where discussions with Arnim Henglein were of great delight to him. He always said that his visits to Bristol University with R. Ottewill and B. Vincent were absolutely necessary in order for him not to go astray in his colloid and surface chemistry. All his life he has enjoyed music and has sung in numerous church choirs, Oratorio, societies, and now in Indiana Opera North. He has returned to his love of boats and now has a sloop on Lake Michigan. His plans for the future as those of the past to follow new ideas with great enthusiasm and establish beautiful concepts in science.
A Brief Description of Research Accomplishments Dr. Thomas’s early research interests lay mainly in the identification of the nature of the interaction of radiation with matter, mainly via the development and utilization of pulse techniques to identify the short-lived intermediates of early radiation events. Over the past two decades, he has utilized the pulsed laser and pulse radiolysis techniques that he developed † All reference numbers used in this section refer to the List of Publications in this issue.
(35†), together with spectroscopic methods, to elucidate the nature of photo and radiation induced processes in aqueous colloidal systems, confined structures, and surfaces and also to comment on the structures of colloids themselves. It is difficult to summarize over 300 publications in this area of research, although a review of the work in 1980 Chemical ReViews (168) and an ACS monograph no. 181 Chemistry of Excitation at Interfaces are included together with a list of
J. Phys. Chem. B, Vol. 103, No. 43, 1999 9057 publications. The material that follows describes highlights of the work together with a few appropriate references. The selected highlights are original developments that have found ready applicability in other laboratories due to their attractiveness and versatility. The work may be conveniently divided into two sections, namely, radiolysis and photolysis in simple homogeneous systems where the techniques are developed, excited states and ions are identified, and the nature of their reactions studied, and also in more complex systems such as micelles, polymers, biosystems, and surfaces. A few selected references that cover each area are listed below. Radiolysis and Photolysis of Simple Systems (35, 37, 54) Development of nanosecond spectroscopic and conduction techniques to study special events and geminate ion recombination of liquids, spectra of excited singlet states, and two photon events such as photoionization. These techniques were the first of the kind reported. The conduction technique (68) led to the first rate constants for e- reactions in nonpolar liquids and to the important development of reactions of quasi-free electrons. The time scale was pushed to the picosecond range later (212) where the nature of formation of excited states with high energy radiation was studied. Micellar and Colloidal Systems Spectroscopic and kinetic studies utilizing the above techniques were used to investigate the molecular environment in colloids; a prime example is the fine structure of pyrene fluorescence (112), solubilization in micelles (135), and transport between water pools in inverted micelles (157). Poisson kinetics were developed to describe chemistry in colloidal systems (82), a technique which, together with that of Turro and Yekta, is now widely used to measure aggregation numbers. Cyclodextrins were used to “coat” reactants and investigate molecular details of reactions (219).
Polyelectrolytes (213, 220, 268, 269) and polymer films have been studied by the above techniques, and in the latter case a “free volume” theory developed to explain diffusion and reaction in polymer films. Films have also been used to investigate details of photoinduced e- tunneling and the effect of phonon coupling on these reactions (218). A summary is given in ref 263. Solid system clays (211), semiconductors (193), zeolites (245), and silica (258) have been used in constrained systems to aid in the elucidation of radiation induced reactions. In particular, the complex reactions of several systems adsorbed on solid surfaces have been understood in a quantitative manner for the first time. Reference 258 describes a unique treatment of “Gaussian” type kinetics to allow for the varied energy states that systems experience on surface. Further works (266, 267, 272, 274, 281) illustrate the many advantages of this new approach. Recently, the fast pulsed techniques in his laboratory have been used to characterize the very fundamental process of initial electron trapping in small water pools (284) and in (Na+) clusters in zeolites (261, 286, 288). Biological Studies Several biological studies in conjunction with other faculty are given in the list of publications which follows. In a nut shell, Dr. Thomas has used his expertise in pulsed techniques of photochemistry and radiation chemistry to make new inroads into the classical and well-established field of colloid chemistry. He has introduced new lines of thought into colloid chemistry along the lines of excited states chemistry, while also awakening photochemists to the utility of colloidal systems in their studies. He originated this area of research on coming to Notre Dame some 20 years ago, and has been active both via his own work and that of his students and ex-students in developing an area of hybrid research which has spread to many laboratories throughout the world. He has been a past Chairman of the Gordon Conference in Radiation Chemistry and of the Gordon Conference on Micelles and Macromolecular Catalysis.
Societies and Memberships British Chemical Society American Chemical Society Radiation Research Society (Editorial Board, 1972-1975; Councillor, 1975-1980) N. Y. Academy of Sciences Photobiology Society Chemical Physics Letters Editorial Board (1980-1986) Journal of Physical Chemistry Editorial Board (1982-1990) Journal of Polymer Science Macromolecules Editorial Board (1990-1994) Journal of Surfaces (1985-) Journal of Colloids & Surfaces (1994-) Awards State Scholarship, 1951 Doctor of Science, 1969 Research Award of the Radiation Research Society, 1974 Fellow of the Royal Society of Chemistry, 1983 Colloid or Surface Chemistry Award of the American Chemical Society sponsored by Procter and Gamble Co., 1993
9058 J. Phys. Chem. B, Vol. 103, No. 43, 1999 Special Honors 1962, 1966, 1970, 1974 1963, 1967, 1974 1963 1968 1968 1969, 1971, 1977, 1994 1970 1971 1971 1971 1974 1975 1976 1976 1977 1977 1977 1977 1977 1979 1979 1975, 1977, 1978, 1979 1982 1982 1982 1983 1983 1983 1983 1983 1984 1986 1986 1987 1987 1988 1989 1989 1988-1989 1990 1993 1995 1995 1997
Invited lectures at the International Congress of Radiation Research Invited lectures at the Gordon Conferences on Radiation Chemistry Invited lecture at the National Academy of Sciences Symposium on Radiobiology Invited lecture at the NATO Symposium on Radiobiology Invited lecture at the American Chemical Society (Petroleum Division) meeting Invited lectures at the Miller Conferences on Radiation Chernistry Lecturer at BAT-SHEVA summer school of fast reactions at Jerusalem Chairman of the Gordon Conference on Radiation Chemistry Member of the Editorial Board of the Journal of Radiation Research American Chemical Society lecturer for student affiliates. Recipient of the Research Award of the Society for Radiation Research American Chemical Society tour speaker Faraday Lecturer at the University of Illinois, Dekalb Invited lecture, American Physical Society: Electron-Transfer Processes Invited lecture at the Gordon Conference on Organic Photochemistry Invited lecture at the Gordon Conference on Micellar Catalysis Councillor in Chemistry for the Radiation Research Society Consultant to Physical Dynamics, Inc., California Consultant to Miles Laboratories, Indiana Editorial Board for Chemical Physics Letters Elected chairman of Gordon Conference on Micellar Catalysis Guest Professor at Hahn Meitner Institute, Berlin Organizer of NSF Solar Energy Conference, Hawaii Editorial Board for the Journal of Physical Chemistry NSF Advisory in Chemistry for the US-Japan Solar Energy Program Chairman, Gordon Conference on Micellar and Macrocatalysis Council for Radiation Research Awards Consultant to Mead Corporation Consultant to Texaco Corporation Consultant to Coming Glass Company Fr. Julius A. Nieuwland, Professor of Chemistry Editorial Board of Journal of Colloid and Interface Science Member of Editor Search Comrnittee for Journal of Radiation Research Consultant to Proctor and Gamble Co. Editorial Board of Langmuir Member NSF Site Visit Group at Rochester University Member Site Visit Group DOE, Berkeley Beverlac Lab Program Comrnittee for Intemational Congress on Radiation Research, Toronto Visiting Professor, University of Bristol, U.K. Editiorial Board of Macromolecules Colloid or Surface Chemistry Award of the American Chemical Society, sponsored by Procter & Gamble Company Visiting Professor, University of Bristol, U.K. Editor of Current Opinions in Colloid Chemistry Member of committee to appoint Editor of Langmuir
K. Kalyanasundaram Michael Graetzel
