Premium
The vibrational structure of the OH radical in solid argon: A transfer‐matrix path‐integral approach
Author(s) -
Costa Cabral B. J.
Publication year - 2005
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20589
Subject(s) - argon , chemistry , matrix (chemical analysis) , dissociation (chemistry) , path integral formulation , ground state , atomic physics , radical , hydroxyl radical , computational chemistry , quantum , physics , quantum mechanics , organic chemistry , chromatography
The vibrational structure of the hydroxyl radical in argon was investigated by transfer‐matrix path‐integral calculations. The results for the OH X 2 Π ground state in Ar indicate that the vibrational structure in the matrix is modified relative to the gas phase. However, only vibrational levels above v = 12 are significantly perturbed. The changes of the higher vibrational energy levels can be explained by interactions between the OH radical and the Ar matrix. We predict that the position of the OH fundamental in argon matrix is 3540 cm −1 in good agreement with the experimental result (3548.2 cm −1 ). This value is red‐shifted by ∼6 cm −1 relative to the free radical (3546 cm −1 ). In contrast with previous results for Br 2 in solid Ar, where a very large barrier related to confinement effects inhibits dissociation, the present study indicates that the OH radical can dissociate in the matrix. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005