’’Proximity effect’’ in radiationless transitions
- 15 January 1978
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 68 (2), 433-454
- https://doi.org/10.1063/1.435775
Abstract
The quantum statistical approach to relaxation phenomena was employed in a numerical investigation of the effect of vibronic interaction between the first and second excited states on the radiationless decay rate of the first excited state. It is shown that the vibronically active out‐of‐plane modes may be the dominant accepting modes for the radiationless transitions of N‐heterocyclics with close‐lying nπ* and ππ* excited states. The decay rate was found to vary with the strength of nπ*–ππ* vibronic interaction, the nπ* and ππ* separation, the energy gap between the initial and final electronic states of the radiationless process, and isotopic substitution, in a manner which is consistent with experimental observation.Keywords
This publication has 12 references indexed in Scilit:
- Zeeman effect of the PMDR signal and the mechanism of the intersystem crossing process in pyrazine at 1.6 KChemical Physics Letters, 1975
- Vibronic coupling and polyatomic spectraChemical Physics Letters, 1975
- Nuclear Coordinate dependence of electronic transition moments in orbitally forbidden transitions: A new interpretation of deuterium isotope effectsChemical Physics, 1975
- The influence of distortions on the nonradiative decay of selectively excited vibronic statesChemical Physics, 1975
- Radiationless transitions in aromatic molecules with nonbonding electrons: Role of vibronically active out-of-plane modesThe Journal of Chemical Physics, 1975
- Electronic spectra and vibronic coupling of pyrazineJournal of Molecular Spectroscopy, 1974
- Second quantization and the general two-centre harmonic oscillator integralsJournal of Physics B: Atomic and Molecular Physics, 1970
- Radiationless Paths in the DiazinesThe Journal of Chemical Physics, 1967
- Electronic states of azabenzenes: A critical reviewJournal of Molecular Spectroscopy, 1967
- Internal conversion in aromatic and N-heteroaromatic moleculesAustralian Journal of Chemistry, 1965