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Analysis of the HOOO torsional potential

Beames, Joseph, Lester, Marsha I., Murray, Craig, Varner, Mychel E. and Stanton, John F. 2011. Analysis of the HOOO torsional potential. Journal of Chemical Physics 134 (4) , 044304. 10.1063/1.3518415

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Abstract

Torsional levels of cis and trans HOOO and DOOO, observed previously via infrared action spectroscopy [E. L. Derro, T. D. Sechler, C. Murray, and M. I. Lester, J. Chem. Phys.128, 244313 (2008)10.1063/1.2945872], have been used in conjunction with ab initio theory to obtain a torsional potential energy surface for the hydrotrioxy radical. High level electronic structure calculations based on the equation-of-motion coupled-cluster method for ionized states (EOMIP-CCSD) are utilized to produce a torsional potential. Eigenvalues of the potential are computed by diagonalizing the torsional Hamiltonian in a free-rotor basis. Uniform scaling of the theoretical potential by a factor of 1.35 yields vibrational frequencies in good agreement with the experiment, and allows prediction of the barrier height to isomerization of ∼340 cm−1 and relative stability of trans-HOOO with respect to cis-HOOO of ∼70 cm−1. Examination of the optimized nuclear coordinates with respect to the torsional angle, suggests that the central O–O bond length is strongly coupled to the torsion and is important in determining the relative stabilities of the two conformers. The scaled potential is then used to determine the torsional contribution to the partition function for atmospheric modeling of HOOO.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: American Institute of Physics
ISSN: 0021-9606
Last Modified: 04 Jun 2017 08:06
URI: http://orca-mwe.cf.ac.uk/id/eprint/72863

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