Abstract

Philip J. Stephens was a theoretical chemist who brought to fruition two new forms of optical spectroscopy, using circularly polarized light, for the determination of electronic structure and molecular stereochemistry. The first was magnetic circular dichroism (MCD), the wavelength dependence of the differential absorption of left and right circularly polarized light induced by a magnetic field applied parallel to the light beam. Stephens established a methodology for extracting from MCD spectra the angular momentum characteristics of ground and excited electronic states and demonstrated applications to the assignment of the optical spectra of coordination complexes of transition metals and to metalloproteins. In the second half of his career Stephens led the field of vibrational circular dichroism (VCD), the measurement of the natural circular dichroism (CD) arising from the vibrational transitions of chiral molecules. He developed instrumental techniques to measure this weak dichroism over a wide frequency range with high sensitivity. Subsequently he developed a quantum-mechanical method that yielded reliable calculations of VCD spectra by using density functional theory. Thus absolute configurations of all the chiral centres in an organic molecule are readily established. Given the increasing importance of enantiomerically pure chiral drugs, VCD has found widespread application in the pharmaceutical industry. Philip had not only a deep understanding of chemical theory but also a thorough grasp of experiments. His lectures on theoretical topics were models of clarity. He was also an accomplished pianist in demand, when a student at Oxford University, as an accompanist and for chamber concerts.

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