The objective in this work has been one which I have shared with the two other 1986 Nobel lecturers in chemistry, D. R. Herschbach and Y. T. Lee, as well as with a wide group of colleagues and co-workers who have been responsible for bringing this field to its current state. That state is summarized in the title; we now have some concepts relevant to the motions of atoms and molecules in simple reactions, and some examples of the application of these concepts. We are, however, richer in vocabulary than in literature. The great epics of reaction dynamics remain to be written. I shall confine myself to some simple stories.

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Some concepts in reaction dynamics.

The transition state region of the F + H(2) reaction has been studied by photoelectron spectroscopy of FH(2)(-). New para and normal FH(2)(-)photoelectron spectra have been measured in refined experiments and are compared here with exact three-dimensional quantum reactive scattering simulations that use an accurate new ab initio potential energy surface for F + H(2). The detailed agreement that is obtained between this fully ab initio theory and experiment is unprecedented for the F + H(2) reaction and suggests that the transition state region of the F + H(2) potential energy surface has finally been understood quantitatively.

https://science.sciencemag.org/content/sci/262/5141/1852.full.pdf

The transition state of the f + h2 reaction.

https://science.sciencemag.org/content/sci/185/4153/739.full.pdf

Tunable Laser Fluorescence Method for Product State Analysis

Energy Distribution Among Reaction Products. VI. F+H 2 , D 2

Relative gain coefficients of individual HF†(DF†) laser transitions in the F + H2, D2, HD chemical lasers have been measured by a grating selection technique. Product vibrational population inversions Nν/Nν−1 were calculated from these measurements. The results indicate a complete parallelism in product vibrational energy content in the four room‐temperature isotopic reactions, modified only by a threshold effect for HF†(ν = 3) production in the F + HD reaction and by secondary mass effects in the HF‐producing VS DF‐producing reactions. A room‐temperature measurement of the intramolecular kinetic isotope effect in the F + HD reaction is reported. Lastly, evidence is presented for highly efficient energy‐transfer processes [V → V′: HF†(ν = 3) + HD(ν = 0) → HF†(ν = 2) + HD†(ν = 1) and E → V: I*(5 2P1/2) + HF†(ν) → I(5 2P3/2) + HF†(ν + 2)].

F + H2, D2, HD reactions: Chemical laser determination of the product vibrational state populations and the F + HD intramolecular kinetic isotope effect

Infra-red emission has been detected from hydrogen fluoride formed in the gas-phase atom-molecule exchange reactions of atomic fluorine with hydrogen and methane. Emission was limited to that from vibrational levels v′ˇ-3 in each case. An extrapolation technique has been used to obtain relative rate constants for direct chemical population of the various vibrational levels. The values found were k 3tk2=0·76, k 2tk1=3·4 for the F + H2 reaction and k 3tk2=0·23, k 2 k 1=3·0 for the F + CH4 case.

Initial vibrational energy distributions determined by infra-red chemiluminescence: I. The reaction of fluorine atoms with hydrogen and methane† This research has been sponsored in part by the Air Force Cambridge Research Laboratories through the European Office of Aerospace Research (OAR), United States Air Force.

Initial vibrational energy level distributions determined by infra-red chemi-luminescence. II. The reaction of fluorine atoms with hydrogen halides

Initial Vibrational Energy Level Populations Resulting from the Reaction H+F2 as Studied by Infrared Chemiluminescence

I.r. emission has been observed from the reactions of atomic oxygen with OCS and CS2 in the 2000–6000 cm–1 region. The mechanisms responsible for production of the vibrationally excited species (represented by †) are discussed and in the case of the OCS reaction, evidence is presented for a stabilization process: O + SO + OCS → SO2+ OCS †.

David H. Slater

Papers

Initial vibrational energy level distributions determined by infra-red chemi-luminescence. II. The reaction of fluorine atoms with hydrogen halides

Initial Vibrational Energy Level Populations Resulting from the Reaction H+F2 as Studied by Infrared Chemiluminescence

Origin of infrared emission from the reactions of atomic oxygen with carbonyl sulphide and carbon disulphide

Ursprung der ir-emission bei der rk. von monosauerstoff mit carbonylsulfid und schwefelkohlenstoff