My Ph. D. thesis at Caltech

My Ph. D. thesis, Chemistry, Caltech, submitted August, 1971 for conferral of degree in the annual convocation in June, 1972.

 

I just re-read this and was very happy to see how much I had learned and synthesized back when.

 

How I got to research at Caltech: I went to Caltech in August, 1966, after finishing my B.S. in Chemistry in 3 years at Notre Dame (a sort of culmination of my decision at age 8 to become a chemist!).  My passion in science was to figure out how chemical reactions work in condensed phases (esp. liquid), from the first principles of physics – scattering theory, molecular electronic structure, and liquid state physics (structure, motions).  I’d already worked on some basic mathematical methods of quantum chemistry with Oliver Ludwig, my NSF undergraduate research advisor.  I’d also had a whirlwind course in all kinds of chemistry (and all the humanities and more) at Notre Dame, advised in depth by the famed Emil T. Hofman, chemist and freshman advisor.  I made many friends at Notre Dame, a number of whom became academic and industrial chemists – Jim Plonka, Dave Greene, among others – and several physicists – Chris Kalmus, for one.  Physical organic chem prof Angelo Lamola suggested that I try Caltech for their graduate program.

I did interview at Princeton for their program but then I read about the molecular beam work being done by Aaron Kuperman.  The chemistry faculty at Caltech sat down all of us new grad students and gave us a mandate to visit all the research groups and find what most intrigued us.  A number of us who also came with the urge to figure out chemical reactions from first principles, including old friend Al Wagner.  The faculty also said, in almost so many words, “You’re chemistry students.  That means you should go to the seminars in engineering, biology, physics ….” And we did.

I also became one of 15 Caltech grad students from all departments to sign up for Richard Feynman’s course in Advanced Quantum Mechanics.  Chutzpah, but we passed!  Two hundred students filled the classroom each day, and the ones who missed a day would ask, “What did he say, what did he say?”  We found that we could reconstruct the lecture almost word-for-word to about halfway, then get a bit hazy without our notes in front of us.  All of us had the experience of walking down the street, even 10 years later, not thinking about physics, when an idea would suddenly crystallize in our head; we’d snap our fingers and say, “So that’s what Feynman meant!”  Feynman was an incredible inspiration, and he was Feynman all the way – in class, in person, in videos.  He encouraged us to work everything out for ourselves rather than read what others had done first, which is mostly to find the other blind alleys.  He also encouraged us to try anything, so that’s a main reason that I’ve done published research in field from quantum chemistry, quantum physics, plant physiology, plant ecophysiology, remote sensing, radiative transport, and more.

 

Caltech was the big push on a great ride in science.  I call it an intellectual candy store.  I had an interesting conversation with David Baltimore, then president of Caltech, ending with my observation, “There’s only one thing wrong with Caltech.”  “Oh, what’s that?”  “After Caltech, everything else  is downhill.”  “Oh, we’re not going to fix that!”

 

I haven’t given credit to enough people, by far, with a view to some brevity. Foremost, I must thank my parents, Vincent William Gutschick and Frances Genevieve Stonich Gutschick, who encourage me, gave me the best schooling opportunities, bought wonderful chemistry equipment and supplies for me, and lived through the fear of a home conflagration at uncertain intervals.  Most welcome additions to our family’s modest means was the support given me by the American Chemical Society, the National Merit Corporation, and the National Science Foundation.  I am extremely fortunate.

 

I just scanned my thesis in 4 PDFs (each about 100 pp or less; there were small edits to this penultimate draft, subsequently).  I hope you might find it interesting, in whole or in part.  At the least, it’s my taste of the heady intellectual world at Caltech, where the diverse fields of science and engineering all met each other.

• 1st PDF (107 pages, 9.5 MB): Title page, dedication, abstract, table of contents; review of liquid state physics and then of the specific theory of critical phenomena in liquid mixtures
• 2nd PDF (98 pages, 5.9 MB): Continuing the theory of critical phenomena in mixtures; the experimental method and analysis of results
• 3rd PDF (46 pages, 2.4 MB): Details of the experimental methods and methods of data analysis
• 4th PDF (79 pages, 6.3 MB): The remaining two big sections of my thesis: quantum mechanical calculation of the electric polarizabilities of small atoms and molecules, and quantum scattering theory calculations of vibrational excitation in collisions of small molecules (H₂)

My thesis had three distinct projects:

• An investigation into the extreme phenomena at the critical point of a liquid mixture, 2,6-lutidine and water. I used the absorption of ultrasonic pulses to delve into the chemical unmixing that soaks up energy near this point.  Though I was a Ph. D. student in Chemistry, I worked in the laboratory of Dr. Cornelius “Neil” Pings in Chemical Engineering.  Caltech profs were always open to having students bridge departments.  In this work, I jumped into deep pools:
  • Experimental work with state-of-the-art equipment and state-of-the-art scientific questions. Besides the odorous mixture, I had the run of high-end oscilloscopes, temperature measurement and control systems, machine shop work, electroplating with silver and gold.
  • Intense theory of liquids in all aspects – their equilibrium properties (equation of state, physical structure) and their transport properties (viscosity, heat conduction, and more) – hence, the first 86 pages of my thesis, in which I reviewed the theory of liquids. What a great adventure.  I followed  this up after I finished and during a few years as an NSF Postdoctoral Fellow at Berkeley and J. W. Gibbs Instructorship at Yale.  A theory using analogy to phonon transport in solids eluded me, alas!
  • The specific theory of Marshall Fixman for the behavior of mixtures at a critical point…and at Yale, later, I worked with Marshall for a year – a wonderful human and a great scientist.
  • Amazing details in electronics, acoustics, and statistics, for analyzing my data.
  • A pool of talent and friendship: lab technician Hollis Reamer was always ready to help, Australian postdoc Tony Collings was a fount of practical and theoretical knowledge
  • Let’s not forget the whole ambience of Caltech, including the library and the bookstore where one can lose oneself with the great minds of the past and the current times. The camaraderie of grad students was also remarkable, even to pranks (as when I suspended plastic fish in the temperature control bath of Hal Strumpf’s study of the critical point of krypton.
• Calculation of the response of small atoms and molecules to an electric field, to estimate the electric polarizability. I modified and extended a classic method, Hartree-Fock, in which one constructs a quantum-mechanical wave function and adjusts coefficients to minimize the electronic energy.  This was the twilight of the Hartree-Fock method, as I now see it; new methods such as density functional theory (nascent then) blow it out of the water, with exquisite accuracy, such that one can calculate the structure and reactivity of molecules before experiments attempt it – a great new way to do chemistry.
  • I did this work in the Noyes Laboratory of Chemical Physics, a new facility at that time, occupied by. My advisor was B. (Basil) Vincent McKoy, a new instructor on his way to becoming a full prof later.  His group and that of Bill Goddard mixed completely, in research, in burgeoning computer knowledge, in lunches every Tuesday at a Mexican restaurant, in volleyball, on trips around the whole area.
  • So, I had two advisors, Vince McKoy in Chemistry and Neil Pings in Chemical Engineering. I’d bring concepts between the groups as we grad students met one evening a week to discuss our research.  The resolution of a quandary in these evening talks came at my Ph. D. oral defense.  Vince McKoy asked if it would be OK to put Jesse Beauchamp, a spectroscopist, on my committee.  I said, “Sure.”  Beauchamp asked me detailed, penetrating questions in the exam.  Three times I had to say, “I don’t know.”  “Guess.”  I did so, correct each time.  “Oh, you know this.”  Lucky!  Afterwards, McKoy told me why he asked for Beauchamp to be on my committee. It seems that, as a first year grad student,  I gave one of those evening talks, presenting the way of describing liquid structure with particle distribution functions, from all N particles down to 2, the pair distribution function from which one can calculate all the thermodynamic properties of the liquid.  Another student said, “Can’t you integrate one more time, to the  singlet distribution function?”  All of us puzzled over than for a quarter hour, reaching no conclusion.  Jesse Beauchamp was there that night and decided that I was an idiot (not really that strongly, though).  McKoy wanted to show him that I really know my stuff, across disciplines.  Only later did I realize that, with the singlet distribution function, all the thermodynamic properties relate to the boundaries, not a useful calculation method at all!
  • All 14 of us in the McKoy-Goddard group used the fine computers that Caltech had, and a few times McKoy bought time on the biggest, baddest machine off-site, the CDC 6600. Programming and data spaces were tight, so we learned very innovative ways to make ultra-compact, highly efficient code. We also learned to do check calculations in our head.  I can still do exponentials in my head.  At times, it’s still useful!
  • All of us, even on NSF fellowships, had to teach at least one semester. The laudable Harry Gray chose that I would be a teaching assistant in his course in Inorganic Chemistry.  That was the area I knew least, so I learned a lot.

 

• Calculating the degree of transfer of collision energy to vibrations of simple H₂ molecules, using quantum scattering theory. Now we’re getting close to chemical reactions!  Certainly, lots of energy exchanges are among translational motion, rotations, and vibrations, with bond-breaking and –making down the line.
  • I fell into the work with fellow McKoy student Dennis Diestler, a vibrant character in his own right.
  • We took a simplified case, head-on collisions. We took a common and useful description of the force between the individual atoms, the Lennard-Jones potential.  We figured out how to describe the different “channels” (combinations of vibrational states of the two molecules) and how to couple them in the collision.  We could then run calculation with quantum scattering theory for a range of energies.
  • The calculations all checked out and the results were rewarding. They gave me my first publication, in the Journal of Chemical Physics that we all regarded so well.
  • In the next few years, Vince McKoy started using quantum scattering theory in his research; Dennis and I had started something.
  • We celebrated our success with several fine dinners at a Dutch Indonesian restaurant in LA, down the Pasadena Freeway. That expanded my experience with novel foods, which I indulge all the time now.
  • More than that: Al Wagner and Al Mortola and I approached the Chemistry Department with the idea that we three would teach a graduate-level course in scattering theory. They let us do so, with a figurehead prof in charge.  We developed hundreds of pages of notes, which I still have, covering wide fields of application.  Al Wagner built our work and his own research into a great career, ending up in his being Associate Director of Argonne National Laboratory, and still doing research to this day, in 2018.

 

Another big break intellectually was my taking the course, Photophysics of Photosynthesis and Vision, taught by brilliant and quirky G. Wilse Robinson…who kept peacocks on his farmette and played the stock market with statistical insight.   He instilled in us a deep intuition on how molecules absorb energy from light, transfer it internally to various modes of motion, and transfer it to other molecules.

• The value of this course became so clear when, in a drought of jobs for chemists, I visited the Los Alamos Scientific Laboratory (before it became the National Laboratory). Lamenting my job prospects, I talked with a friend who suggested that I contact George Bell and Walter Goad, who were starting a new group, Theoretical Biology, T-10.
• They hired me! Oddly, in my job interview, I presented work I had done on the theory of energy transfer in photosynthesis, choosing that over studies I’d taken up on theoretical immunology.  I figure no one in T-10 was doing the latter.  Actually, they all were, except Walter Goad and I.
• It all mushroomed from there, with my getting very deeply into photosynthesis, biological nitrogen fixation, plant physiology, and beyond. To get oriented into just how plants are structured and how they function, I took the advice of a friend to talk to Lou Ellen Kay, finishing a Ph. D. in Biology from the City University of New York, under a program of the Associated Western Universities of the US by which students could do their research at national labs.  To be succinct, we fell in love, got married, had a wonderful son, David, who just finished his Ph. D at Ohio State, traveled to 40 countries, moved to Las Cruces, had time living overseas, and ended up truly enjoying life.