Spectroscopy of SH (A–X) transition in Ar and Kr matrices: The caging of predissociation

Autor:	J. Zoval, V. A. Apkarian, Dan G. Imre
Rok vydání:	1993
Předmět:	Chemistry Krypton Relaxation (NMR) Matrix isolation General Physics and Astronomy chemistry.chemical_element Fluorescence Molecular physics Spectral line Bond length Computational chemistry Physical and Theoretical Chemistry Spectroscopy Excitation
Zdroj:	The Journal of Chemical Physics. 98:1-7
ISSN:	1089-7690 0021-9606
Popis:	The A(2Σ+)–X(2Π) transition of SH isolated in Ar and Kr matrices is studied by laser induced fluorescence spectroscopy. The (0,0), (1,0), and (2,0) transitions are observed in excitation. These lines are structureless and homogeneously broadened (200–300 cm−1). The (0,0), (0,1), and (0,2) emission bands, are strongly Stokes shifted and further broadened (≥1000 cm−1). The spectra can be successfully interpreted in analogy with OH–Rg pair interactions. The SH(A)–Rg potential is deeply bound (∼1000 cm−1 in Ar and ∼2000 cm−1 in Kr) with nearly 1 A compression along this coordinate. Franck–Condon analysis indicates that the equilibrium bond length of SH(A) is 0.055 A longer than in the free radical. The A state, which is strongly predissociated in the free radical, relaxes radiatively in the matrix: τ=425 and 770 ns in Ar and Kr, respectively. Predissociation is treated as a two‐dimensional tunneling process between two electronic surfaces. Poor Franck–Condon factors along the solvent coordinate, due to differ...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::cdb53a8255fac5fa96898c84cb983bd9 https://doi.org/10.1063/1.464654 Zobrazit plný text záznamu