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A study of the mode-selective trans-cis isomerization in HONO using ab initio methodology

Abstract : Ab initio calculations on the six-dimensional cis-trans double minimum potential energy surface of the electronic ground state of the HONO molecule were performed using a coupled cluster approach. An analytic fit to the data points was established. The interconversion barrier was calculated to be 4105 cm(-1). The nuclear motion problem was solved variationally using a full six-dimensional Hamiltonian in internal coordinates. The eigenstates up to about 3650 cm(-1) were tentatively assigned by harmonic quantum numbers. The assignment was based on the mean values of the internal coordinates of the six-dimensional eigenfunctions and on a comparison of the eigenenergies with those calculated by second-order perturbation theory from a full quartic force field in dimensionless normal coordinates. In cold matrices the trans- and the cis-OH nu(1) stretching modes and the first trans- and cis-NO 2nu(2) stretching overtones lead to isomerization. In the isolated molecule these modes (J=0) were found to be entirely localized. However, several overtones of the nu(4) ONO bending and nu(5) N-O stretching, which are close in energy to the OH stretch and combined with the torsional mode, were found to be strongly cis-trans delocalized. (C) 2004 American Institute of Physics.
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Submitted on : Wednesday, May 2, 2012 - 4:47:28 PM
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F. Richter, M. Hochlaf, P. Rosmus, F. Gatti, H. D. Meyer. A study of the mode-selective trans-cis isomerization in HONO using ab initio methodology. Journal of Chemical Physics, American Institute of Physics, 2004, 120 (3), pp.1306--1317. ⟨10.1063/1.1632471⟩. ⟨hal-00693444⟩



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