Vibronic Interaction of Nearly Degenerate States in Substituted Benzene Anions
- 1 October 1965
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 43 (7) , 2187-2199
- https://doi.org/10.1063/1.1697109
Abstract
The pseudo‐Jahn—Teller effect, the vibronic interaction of nearly degenerate electronic states, arises in the same manner as the Jahn—Teller effect itself. An iteration method, suitable for desk calculation, has been developed to allow computation of the vibronic wavefunctions and energies of a system with two closely spaced electronic states. A calculation on benzene anion compares favorably with previously published results. The method, in combination with semiempirical evaluation of the necessary parameters, has been applied to various substituted benzene anions and the ESRspectra of these anions predicted. The results compare satisfactorily with experiment and indicate that the spectra are the net result of three principal factors, configuration interaction among the simple molecular orbital electronic states, vibronic coupling, and thermal equilibrium between at least two vibronic states.Keywords
This publication has 30 references indexed in Scilit:
- Orbital Degeneracy and the Electron Spin Resonance Spectrum of the Benzene-1-d Negative IonJournal of the American Chemical Society, 1964
- The Coupling of Vibrational and Electronic Motions in Degenerate and Nondegenerate Electronic States of Inorganic and Organic Molecules: Part III. Nondegenerate Electronic StatesPublished by Wiley ,1963
- Quantum Theory an Essay on Higher-Order Vibronic InteractionsAnnual Review of Physical Chemistry, 1962
- Temperature Dependence of Proton Hyperfine SplittingsJournal of the American Chemical Society, 1962
- The alternation of bond lengths in long conjugated chain moleculesProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1959
- The Electronic Spectrum of Aromatic Molecules VI: The Mesomeric EffectProceedings of the Physical Society. Section A, 1955
- The force field, vibration frequencies, normal co-ordinates, infra-red and Raman intensities for benzenePhilosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences, 1955
- Ionization potentials and electron affinities of conjugated hydrocarbon molecules and radicalsTransactions of the Faraday Society, 1955
- The Thermodynamics and Molecular Structure of Benzene and Its Methyl Derivatives1Journal of the American Chemical Society, 1943
- ASYMMETRIC VIBRATIONS EXCITED BY AN ELECTRONIC TRANSITIONAnnals of the New York Academy of Sciences, 1941