Fitting of a PES for rovibrational calculations on $NO_{2}$

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Title: Fitting of a PES for rovibrational calculations on $NO_{2}$
Creators: Schryber, Jeremy H.; Polyansky, Oleg L.; Tennyson, Jonathan; Jensen, Per
Issue Date: 1996
Publisher: Ohio State University
Abstract: We took the potential energy surface for the ground electronic state of $NO_{2}$ constructed by Tashkun and $Jensen^{a}$ using the MORBID Hamiltonian and computer program. We wished to fit this experimental date using the exact kinetic energy (EKE) operator. Initially, EKE calculations were not not possible due to the presence of holes in the surface. A better starting point for the fit was constructed using the method in Polyansky $et al^{b}$ whereby MORBID and EKE calculations are combined. We then improved the surface by fitting it to available experimental data using an iterative least-squares fitting procedure. In the low-energy region ($<10,000$ $cm^{-1}$) the fitting was successful. Above apporximately $10,000 cm^{-1}$ the higher electronic state begins to peturb the vibrational energy levels of the ground state. We were unable to fit the surface well to the experimental date above $10,000 cm^{-1}$. We aim to provide a surface which will give accurate rovibrational levels of $NO_{2}$.
Description: $^{a}$S.A. Tashkun and P. Jensen, J. Mol. Spec., 165, 173-184 (1994). $^{b}$O.L. Polyansky, P. Jensen and J. Tennyson, J. Chem. Phys., 101, 7651-7657 (1994)
Author Institution: Department of Physics and Astronomy, University College London; Physikaliach-Chemisches Institut, Justus-Lieting-Universit\""{a}t Giessen
Other Identifiers: 1996-TC-03
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