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Vibrational structure in atomic emission spectra: Hg atoms in molecular matrices

Journal of Chemical Physics, ISSN: 0021-9606, Vol: 107, Issue: 7, Page: 2205-2214
1997
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Mercury atoms excited to the P state in rare gas and molecular (CH, CD, CF, and SF) matrices relax by a direct P→S fluorescence with a ca. 60 ns lifetime or by the P-/\/\/\>P radiationless transition followed by the P→S long-lived (τ in the 10 to 500 ms range) emission. The main difference between atomic and molecular hosts is the appearance, in the latter case, of a well resolved vibrational structure in the spectrum of the P→S transition involving the frequencies of nontotally symmetric modes of the host molecules. This structure, related to a shortening of the lifetime of the P→S emission is explained by the intensity borrowing from the allowed P→S transition, i.e., by the P↔P mixing induced by nontotally symmetric vibrations of neighbor molecules (analog of the Herzberg-Teller effect). Relative intensities of bands corresponding to different vibrational modes may be deduced from estimation of electric fields induced in the Hg atom by displacements of electric charges of the vibrating molecule © 1997 American Institute of Physics.

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