The vibrational structure of the OH radical in solid argon: A transfer-matrix path-integral approach

摘要

The vibrational structure of the hydroxyl radical in argon was investigated by transfer-matrix path-integral calculations. The results for the OH X(2)Pi 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 similar to 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. (c) 2005 Wiley Periodicals, Inc.