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Rovibrational energy levels of hydrogen peroxide, studied by MULTIMODE with a reaction path Hamiltonian

Carter, S. and Handy, N.C. (2004) Rovibrational energy levels of hydrogen peroxide, studied by MULTIMODE with a reaction path Hamiltonian. Spectrochimica Acta Part A, 60 (8-9). pp. 2107-2111. ISSN 1386-1425

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To link to this item DOI: 10.1016/j.saa.2003.11.016

Abstract/Summary

Recently. Carter and Handy [J. Chem. Phys. 113 (2000) 987] have introduced the theory of the reaction path Hamiltonian (RPH) [J. Chem. Phys. 72 (1980) 99] into the variational scheme MULTIMODE, for the calculation of the J = 0 vibrational levels of polyatomic molecules, which have a single large-amplitude motion. In this theory the reaction path coordinate s becomes the fourth dimension of the moment-of-inertia tensor, and must be treated separately from the remaining 3N - 7 normal coordinates in the MULTIMODE program. In the modified program, complete integration is performed over s, and the M-mode MULTIMODE coupling approximation for the evaluation of the matrix elements applies only to the 3N - 7 normal coordinates. In this paper the new algorithm is extended to the calculation of rotational-vibration energy levels (i.e. J > 0) with the RPH, following from our analogous implementation for rigid molecules [Theoret. Chem. Acc. 100 (1998) 191]. The full theory is given, and all extra terms have been included to give the exact kinetic energy operator. In order to validate the new code, we report studies on hydrogen peroxide (H2O2), where the reaction path is equivalent to torsional motion. H2O2 has previously been studied variationally using a valence coordinate Hamiltonian; complete agreement for calculated rovibrational levels is obtained between the previous results and those from the new code, using the identical potential surface. MULTIMODE is now able to calculate rovibrational levels for polyatomic molecules which have one large-amplitude motion. (C) 2003 Elsevier B.V. All rights reserved.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11083
Uncontrolled Keywords:rovibrational energy levels, variation theory, reaction path Hamiltonian, large-amplitude motion, peroxide , LARGE-AMPLITUDE MOTION, AB-INITIO, VIBRATIONS, FORMALDEHYDE, MOLECULES

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