William A. Klemperer (October 6, 1927 – November 5, 2017) was an American chemist who was one of the most influential chemical physicists and molecular spectroscopists in the second half of the 20th century. Klemperer is most widely known for introducing molecular beam methods into chemical physics research, greatly increasing the understanding of nonbonding interactions between atoms and molecules through development of the microwave spectroscopy of van der Waals molecules formed in supersonic expansions, pioneering astrochemistry, including developing the first gas phase chemical models of cold molecular clouds that predicted an abundance of the molecular HCO+ ion that was later confirmed by radio astronomy.
William Klemperer (captured by Stewart Novick, ca. 1970)
|Born||6 October 1927|
New York City, United States
|Died||5 November 2017(aged 90)|
|Alma mater||Harvard University (A.B.), University of California, Berkeley (Ph.D.)|
|Doctoral advisor||George C. Pimentel|
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Bill Klemperer was born in New York City in 1927 and was raised there and in New Rochelle. His parents were both Physicians. He graduated from New Rochelle High school in 1944 and then enlisted in the U.S. Navy Air Corps, where he trained as a tail gunner. He obtained an A.B. from Harvard University in 1950, majoring in Chemistry, and then headed to the University of California, Berkeley, where in early 1954 he obtained a Ph.D. in Physical Chemistry under the direction of George C. Pimentel. After one semester as instructor at Berkeley, Bill returned to Harvard in July 1954.
Klemperer's initial appointment was an instructor of analytical chemistry, but he quickly rose through the ranks and was appointed full professor in 1965. He has remained associated with Harvard Chemistry throughout his long career. He spent 1968-69 on sabbatical with the Astronomers at Cambridge University and 1979-81 as Assistant Director for Mathematical and Physical Sciences at the U.S. National Science Foundation. He was a visiting scientist at Bell Laboratories during a time when it was the premier industrial laboratory. Klemperer became an emeritus professor in 2002 but remained active in both research and teaching.
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Klemperer's early work concentrated on the infrared spectroscopy of small molecules that are only stable in the gas phase at high temperatures. Among these are the alkali halides, for many of which he obtained the first vibrational spectra. The work provided basic structural data for many oxides and fluorides, and gave remarkable insight into the details of the bonding. It also led Klemperer to recognize the immense potential of molecular beams in spectroscopy, and in particular the use of the electric resonance technique to address fundamental problems in structural chemistry. An important result was his benchmark measurement of the electric dipole moment of LiH, at a date when this was the largest molecule for which quantum chemical calculations had any hope of getting useful results in a sensible length of time. Klemperer has always been enthusiastic about molecular beams; he writes: "Molecular beams are fun for a chemist. They give one a sense of power."
An example of this is the use that Klemperer and his students made of electric deflection methods to determine the polarities of a number of high temperature species; the results were unexpected, and to everyone's surprise it turned out that half the alkaline earth dihalides are polar, meaning they cannot be symmetric linear molecules, contrary to the simple and widely taught models of ionic bonding. Klemperer also provided precise dipole moments of excited electronic states both by using the Stark effect in electronic spectra and by using electric resonance spectroscopy of metastable states of molecules.
Klemperer introduced the technique of supersonic cooling as a spectroscopic tool, which has dramatically increased the intensity of molecular beams and also greatly simplified the spectra. This innovation has been second only to the invention of the laser in its impact on high-resolution spectroscopy.
Klemperer helped to found the field of interstellar chemistry. In interstellar space, densities and temperatures are extremely low, and all chemical reactions must be exothermic, with no activation barriers. The chemistry is driven by ion-molecule reactions, and Klemperer's modeling of those that occur in molecular clouds has led to a remarkably detailed understanding of their rich highly non-equilibrium chemistry. Klemperer assigned HCO+ as the carrier of the mysterious but universal "X-ogen" radio-astronomical line at 89.6 GHz, which had been reported by D. Buhl and L.E. Snyder.
Klemperer arrived at this prediction by taking the data seriously. The radio telescope data showed an isolated transition with no hyperfine splitting; thus there were no nuclei in the carrier of the signal with spin of one or greater nor was it a free radical with a magnetic moment. HCN is an extremely stable molecule and thus its isoelectronic analog, HCO+, whose structure and spectra could be well predicted by analogy, would also be stable, linear, and have a strong but sparse spectrum. Further, the chemical models he was developing predicted that HCO+ would be one of the most abundant molecular species. Laboratory spectra of HCO+ (taken later by Claude Woods et al.,) proved him right and thereby demonstrated that Herbst and Klemperer's models provided a predictive framework for our understanding of interstellar chemistry.
The greatest impact of Klemperer's work has been in the study of intermolecular forces, a field of fundamental importance for all of molecular- and nano-science. Before Klemperer introduced spectroscopy with supersonic beams, the spectra of weakly bound species were almost unknown, having been restricted to dimers of a few very light systems. Scattering measurements provided precise intermolecular potentials for atom–atom systems, but provided at best only limited information on the anisotropy of atom–molecule potentials.
He foresaw that he could synthesize dimers of almost any pair of molecules he could dilute in his beam and study their minimum energy structure in exquisite detail by rotational spectroscopy. This was later extended to other spectral regions by Klemperer and many others, and has qualitatively changed the questions that could be asked. Nowadays it is routine for microwave and infrared spectroscopists to follow his "two step synthesis" to obtain the spectrum of a weakly bound complex: "Buy the components and expand." Klemperer quite literally changed the study of the intermolecular forces between molecules from a qualitative to a quantitative science.
The dimer of hydrogen fluoride was the first hydrogen bonded complex to be studied by these new techniques, and it was a puzzle. Instead of the simple rigid-rotor spectrum, which would have produced a 1 – 0 transition at 12 GHz, the lowest frequency transition was observed at 19 GHz. Arguing by analogy to the well known tunneling-inversion spectrum of ammonia, Klemperer recognized that the key to understanding the spectrum was to recognize that HF – HF was undergoing quantum tunnelling to FH – FH, interchanging the roles of proton donor and acceptor.
Each rotational level was split into two tunneling states, with an energy separation equal to the tunneling rate divided by Planck's constant. The observed microwave transitions all involved a simultaneous change in rotational and tunneling energy. The tunneling frequency is extremely sensitive to the height and shape of the inter-conversion barrier, and thus samples the potential in the classically forbidden regions. Resolved tunneling splittings proved to be common in the spectra of weakly bound molecular dimers.
Bill Klemperer has had many awards and honors, which include:
- Inducted a Fellow of the American Physical Society, 1954
- Elected to the American Academy of Arts and Sciences, 1963
- Elected to the National Academy of Science, 1969
- John Price Wetherill Medal, awarded by the Franklin Institute, 1978
- Irving Langmuir Award, awarded by the American Chemical Society, 1980
- The Distinguished Service Medal, awarded by the U.S. National Science Foundation, 1981
- The Earle K. Plyler Prize for Molecular Spectroscopy, awarded by the American Physical Society, 1983
- The Bomem-Michelson Award for the advancement of the field of vibrational spectroscopy. awarded by the Coblentz Society, 1990
- Inaugural George C. Pimentel Memorial Lecturer, Chemistry Department, UC Berkeley. 1991-2.
- The Remsen Award from the Maryland Section of the American Chemical Society, 1992
- The Peter Debye Award in Physical Chemistry, awarded by the American Chemical Society, 1994
- The Faraday Medal and Lectureship from the Royal Society of Chemistry (England), 1995
- Honorary Doctor of Science from the University of Chicago, 1996
- Honorary Citizen of Toulouse, France, 2000
- E. Bright Wilson Award in Spectroscopy from the American Chemical Society, 2001
- "Remembering William Klemperer". chemistry.harvard.edu. Retrieved 20 December 2017.
- W. Klemperer (1955)."Infrared Spectrum of LiH", Journal of Chemical Physics 23, 2452.
- W. Klemperer (1995). "Some Spectroscopic Reminiscences" , Annual Reviews in Physical Chemistry 46, 1
- A. Buchler, J.L. Stauffer and W. Klemperer (1964). "The Determination of the Geometry of High Temperature Species by Electric Deflection and Mass Spectrometric Detection", Journal of the American Chemical Society 86, 4544.
- D.E. Freeman and W. Klemperer (1964). "Dipole Moments of Excited Electronics States of Molecules: The 1A2 State of Formaldehyde", Journal of Chemical Physics 40 604 (1964).
- R.C. Stern, R.H. Gammon, M.E. Lesk, R.S. Freund and W. Klemperer (1970). "Fine Structure and Dipole Moment of Metastable a3Π Carbon Monoxide", Journal of Chemical Physics 52, 3467.
- S.E. Novick, P.B. Davies, T.R. Dyke and W. Klemperer (1973). "Polarity of van der Waals Molecules",Journal of the American Chemical Society 95 8547.
- E. Herbst and W. Klemperer (1973). "The Formation and Depletion of Molecules in Dense Interstellar Clouds", The Astrophysical Journal 185, 505.
- W. Klemperer (1970). "Carrier of the Interstellar 89.190 GHz Line", Nature 227, 1230.
- D. Buhl and L.E. Snyder (1970). "Unidentified Interstellar Microwave Line", Nature 228, 267.
- R.C. Woods, T.A. Dixon, R.J. Saykally, and P.G. Szanto (1975). "Laboratory Microwave Spectrum of HCO+", Physical Review Letters 35, 1269.
- T.R. Dyke, B.J. Howard and W. Klemperer (1972). "Radio Frequency and Microwave Spectrum of the Hydrogen Fluoride Dimer: A Nonrigid Molecule", Journal of Chemical Physics 56, 2442.