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A reaction surface Hamiltonian study of malonaldehyde

Tew, D.P., Carter, S. and Handy, N.C. (2006) A reaction surface Hamiltonian study of malonaldehyde. Journal of Chemical Physics, 125 (8). 084313. ISSN 0021-9606

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To link to this item DOI: 10.1063/1.2338891

Abstract/Summary

We report calculations using a reaction surface Hamiltonian for which the vibrations of a molecule are represented by 3N-8 normal coordinates, Q, and two large amplitude motions, s(1) and s(2). The exact form of the kinetic energy operator is derived in these coordinates. The potential surface is first represented as a quadratic in Q, the coefficients of which depend upon the values of s(1),s(2) and then extended to include up to Q(6) diagonal anharmonic terms. The vibrational energy levels are evaluated by solving the variational secular equations, using a basis of products of Hermite polynomials and appropriate functions of s(1),s(2). Our selected example is malonaldehyde (N=9) and we choose as surface parameters two OH distances of the migrating H in the internal hydrogen transfer. The reaction surface Hamiltonian is ideally suited to the study of the kind of tunneling dynamics present in malonaldehyde. Our results are in good agreement with previous calculations of the zero point tunneling splitting and in general agreement with observed data. Interpretation of our two-dimensional reaction surface states suggests that the OH stretching fundamental is incorrectly assigned in the infrared spectrum. This mode appears at a much lower frequency in our calculations due to substantial transition state character. (c) 2006 American Institute of Physics.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11662
Uncontrolled Keywords:VIBRATION-ROTATION INTERACTION, RAY PHOTOELECTRON-SPECTROSCOPY, INTRAMOLECULAR HYDROGEN-BOND, LARGE-AMPLITUDE MOTION, POLYATOMIC-MOLECULES, PROTON-TRANSFER, INFRARED-SPECTRUM, ATOM TRANSFER, PATH, energy harvest

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