Autobiography of Joe V. Michael - The Journal of Physical Chemistry A

Jul 16, 2015 - This article is part of the 100 Years of Combustion Kinetics at Argonne: A Festschrift for Lawrence B. Harding, Joe V. Michael, and Alb...
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Special Issue Preface pubs.acs.org/JPCA

Autobiography of Joe V. Michael

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Chemical Sciences. Klemm was a former postdoc with Lou and had also built a FP-RF apparatus for combustion kinetics studies at Brookhaven. Klemm wanted to expand capabilities, particularly the T-range, using both FP-RF and a discharge flow system with resonance fluorescence (DF-RF) detection. He had already tested a quartz reaction tube. In the summers of 1978, 1979, and 1980, he invited me to come to Brookhaven for one month and help calibrate the entire discharge flow system and measure the bimolecular rate constant for O + H2CO, H + methanol, and H + neopentane. Klemm suggested that I apply for a co-PI position in Applied Science at BNL to work on both the FP-RF and the DF-RF apparatuses. My collaborators on these projects were Klemm, E. G. Skolnik, T. Tanzawa, and D. G. Keil (one of my best Ph.D. students). The managers at DOE, Chemical Sciences (who had been managers of the AEC project that had supported my research for nine years at CMU), approved the position, and I started work at BNL in March of 1981. It was a great pleasure to work with Keil again since he was and is a gifted scientist. We also adapted the equipment to measure OH-radical abstraction reactions (OH + acetaldehyde). Kiel’s contract was nearly finished by then, and it was not continued. Because we wanted to reach combustion temperatures, we built a shock tube and used atomic resonance absorption spectrometric (ARAS) detection. My former graduate student, T. C. Schwab, had worked on both boundary layer corrections and line absorption calculations. This experience was invaluable in the design and operation of the new equipment. We incorporated VUV flash photolysis to create atoms in reflected waves that we could detect using ARAS. Using this FP-ST method, we measured rate constants for H + NH3. The technician in the group was J. Barry, and his advice and help in construction was also invaluable. J. Sutherland, another PI in the Applied Science Division, joined the group in 1984 specifically to work on the shock tube project. When I started at BNL, I suggested to my wife that we relocate to Long Island. She did not want to move again. I asked her if she wanted to divorce. She agreed. This was not a good time for anyone, especially our children. It took about 3.5 years to work out the details, and the divorce was amicable and was finalized in late 1985. My major outside hobby was singing tenor in about five musical groups on Long Island (including North Shore United Methodist Church), and at church, I met a young woman, Valerie M. Efimetz, who was divorcing her husband. They had a 4-year old son (Derek Paul Efimetz, December, 1980). We began seeing more and more of one another, culminating in a proposal of marriage (September, 1986). We were married in late November, 1986. This was the best decision that both Val and I ever made in our lives.

was born October 2, 1935, in Indiana. I had three older brothers and one younger sister. After graduating from highschool in 1953, I attended a liberal arts college, Wabash College, graduating in 1957. In 1958, I then went to graduate school in Chemistry at the University of Rochester working with W. A. Noyes, Jr. My thesis title was the Photochemistry of Methyl Amine. I met Judith Saunders Lake, another first year graduate student working with Noyes, and we were married in 1960. We defended our theses in 1962, and I began a two-year postdoc with G. B. Kistiakowsky at Harvard working on a shock tube coupled to a time-of-flight mass spectrometer. Our first daughter (Susan Elizabeth, November, 1963) was born. We then moved for one year to Brookhaven National Lab on Long Island where we (R. E. Weston, Jr.) first used atomic resonance absorption as a detection method for doing gas kinetics. Our second daughter was born (Jane Eileen, August, 1965), and we then moved from Brookhaven to Pittsburgh and The Carnegie Institute of Technology where I had accepted a position as Assistant Professor of Chemistry. In 1967, Carnegie Tech merged with Mellon Institute becoming Carnegie-Mellon University (CMU). A year later, our son was born (Jonathan Victor, May, 1968). I taught for ten years at CMU and supervised ten graduate students; nine Ph.D.’s and one M.S. All have had successful careers in teaching, research, business, administration, and/or government. The work was continually supported by the same agency, the U.S. Atomic Energy Commission (AEC). In ten years, we published ∼2.5 articles/year in refereed journals. In 1975, Lou Stief asked me if I would be interested in a 2 year NAS/NRC Senior Resident Research Associate Position in Lou’s Lab at NASA/Goddard Space Flight Center. I applied and the appointment was funded. I started work in December, 1975. Lou had built a Flash Photolysis-Resonance Fluorescence (FP-RF) apparatus with temperature control (200−500 K) and was using it to measure atoms with molecule rate constants to support the NASA/Planetary Atmospheres Program. My associate’s position would be terminating soon, so we decided to illustrate the flexibility of the equipment by measuring Clatom rate constants. This had become an important issue since the Rowland and Molina announcement of the damaging effects of uncontrolled releases of chlorofluoromethanes. We were eventually included in NASA funding awards that Lou used to support me for another 4.3 years as a Visiting Professor of Chemistry at the Catholic University of America. During my stay, sabbaticals were taken by three faculty members. The project supported three permanent staff members, two postdocs, and two graduate students. These researchers were all highly motivated and competent. I really appreciated working with Lou and his group. We did well supplying quite a number of results for the chemical modeling of atmospheres of planets and moons in the solar system. We published about 5.4 papers/year in refereed journals. In 1979, I met R. B. Klemm, a chemist in the Department of Applied Science at Brookhaven National Laboratory who was supported by the U.S. Department of Energy, Office of © 2015 American Chemical Society

Special Issue: 100 Years of Combustion Kinetics at Argonne: A Festschrift for Lawrence B. Harding, Joe V. Michael, and Albert F. Wagner Published: July 16, 2015 7084

DOI: 10.1021/acs.jpca.5b01880 J. Phys. Chem. A 2015, 119, 7084−7085

The Journal of Physical Chemistry A

Special Issue Preface

constants for methylated esters as surrogates for biofuels. We also measured H/D + methylated esters and CH3 + ethane, ethylene, and acetylene. We are continuing work on branching ratios in high temperature abstractions. Looking back on our accomplishments, I would like to give credit to my mentors who were always fascinated by results and gave the pleasurable impression that the results being considered were of great value. That attitude hooked students into teaching and chemical research as their career choice, and in my case, this was certainly true. As a mentor to graduate students, I also emphasized the pleasure of discovery, and I am proud of their accomplishments. I soon found out that I was being increasingly taught rather than being the one who teaches. This effect was even more evident in “advising” postdoctoral students. Every one of them contributed to the success of the program in experiment design, instrumentation, data analysis, and theoretical understanding. They all became better and better scientists during their time at Argonne. Regarding collaborators, I have simply been amazed at the number of scientists who have participated in the work. I thank them all. But I would like to especially thank L. J. Stief for his timely invitation to work at the Goddard Space Flight Center. I would additionally like to express my appreciation to the late R. B. Klemm and to J. W. Sutherland from Brookhaven National Laboratory. Sutherland’s contributions were invaluable both at Brookhaven but also at Argonne where he continued chemical research for another few years after retiring from Brookhaven. I would also like to thank M.-C. Su, a long-time collaborator currently at Sonoma State University, who has held summer appointments over the course of 20+ years. Lastly, I thank each of the members in the Dynamics in the Gas Phase group at Argonne (M. J. Davis, Y. Georgievski, L. B. Harding, S. J. Klippenstein, S. T. Pratt, K. Prozument, B. Ruscic, R. Shepard, R. Sivaramakrishnan, R. S. Tranter, and A. F. Wagner, and retired members R. G. Macdonald and J. P. Hessler) for their past and future interaction with our experimental results. I think we are succeeding in our original goal of experimental to theoretical comparisons.

We continued FP-ST studies on six reactions, demonstrating that flash photolysis coupled to ARAS in reflected shock waves offers a method for measuring absolute rate constants at combustion temperatures. Of course, this demonstration was one of our original goals. In late May, 1986, I attended the DOE Combustion Contractor’s meeting at Airlie, VA and heard that Argonne National Laboratory was requesting additional DOE funds to expand the existing theoretical group with experimentalists, the goal being that both theory and experiment could then be compared within the group. This idea had widespread support from many people including DOE project managers. I met the Argonne theory group leader, Th. Dunning and also Al Wagner and was asked to give a seminar at Argonne. The possibility of joining a group that features both experiment and theory really appealed to me since, in most of my previous work, I paid attention to theory even though I was never good at it. Though the interview was quite positive, nothing happened until after the start of the new year. There were some support issues, but somehow funding was resolved. In early spring of the next year, Dunning called offering me a position to start in May. We moved to Illinois the first week in May, and I started work on May 7, 1987. Renovated lab space became available by midAugust. I had earlier proposed building a 4 in. diameter shock tube, making boundary layer corrections less important than at BNL (2 in. diameter tube). I ordered parts and constructed the apparatus by myself. Preliminary experimentation started in early November. I submitted a paper on O + D2 for publication in July, 1988 (including a theoretical discussion of isotope effects), and a second paper with Al Wagner on O + C2H2 and C2D2 later in the year. 1990 was a productive year. With postdocs, J. R. Fisher and K. S. Shin, ten papers, including studies on H/D + D2/H2, were published and/or submitted. Theoretical studies by colleagues from Emory University followed. The temperature-dependent rate constants for several additional reactions were measured, but Fisher and Shin both found permanent positions and resigned after a few months (replaced by K. P. Lim). Our son (Eugene Stewart, December, 1990) was born. He is the joy of our later years. With Lim, S. S. Kumaran, J. Hranisavljevic, J. J. Carroll, and N. K. Srinivasan over the next 17 years, we measured thermal uni- and bimolecular rate constants for about 50 reactions. To measure both types of rate constants, we developed the ARAS method for Cl-, Br-, I-, and N-atoms. We also developed multipass absorption for detecting OH-, CF2-, and CH3radicals, and with these techniques we continued rate constant determinations. In a majority of studies we closely collaborated with our theoretical colleagues. In 2003 we contributed to a hallmark study, in collaboration with Mielke, Truhlar, and associates, on the convergence of experiment and theory for the simplest bimolecular reaction, H + H2. Starting ∼2008, we concentrated on OH reactions, particularly OH + hydrocarbons, in an attempt to understand the reactivity for primary vs secondary vs tertiary abstractions. Comparing experiment with high-level electronic structure theory, Sivaramakrishnan was able to develop an improved group method for predicting abstraction rate constants for OH + n-saturated hydrocarbons. For several cases, we also made measurements on roaming pathways in dissociation reactions prompted by L. B. Harding. We measured D + molecule reactions as surrogates for H atom reactions. With Peukert, we measured decomposition rate

Joe V. Michael

7085

DOI: 10.1021/acs.jpca.5b01880 J. Phys. Chem. A 2015, 119, 7084−7085