Vibrational relaxation in the lowest electronically excited state of N in solid Kr and Xe
The Journal of Chemical Physics, ISSN: 0021-9606, Vol: 98, Issue: 9, Page: 6965-6974
1993
- 23Citations
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- Citations23
- Citation Indexes23
- CrossRef23
- 21
Article Description
Vibrational relaxation in the A Σ state of N in rare gas matrices has been investigated by selective excitation with an excimer pumped and frequency doubled dye laser system combined with stimulated anti-Stokes Raman scattering. The relaxation is dominated at high N concentrations of some percent by nonresonant electronic energy transfer to other randomly distributed N molecules and at low concentrations by multiphonon processes. The relaxation by energy transfer can be described with the Förster-Dexter model and exchange interaction. Time resolved data are compared with calculated configuration averaged rate constants. The multiphonon processes can compete with energy transfer only if the N-N spacings exceed several lattice constants. The multiphonon rate constants are comparable to the radiative ones in Kr but are much smaller than the radiative ones in Xe. The increase in radiative rate constants with vibrational quantum number is explained by a stronger mixing with the host excitons due to a better energy resonance. © 1993 American Institute of Physics.
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