Are ab initio quantum chemistry methods able to predict vibrational states up to the dissociation limit for multi-electron molecules close to spectroscopic accuracy?

Péter G. Szalay; Filip Holka; Julien Fremont; Michael Rey; Kirk A. Peterson; Vladimir G. Tyuterev

doi:10.1039/C0CP01334J

Are ab initio quantum chemistry methods able to predict vibrational states up to the dissociation limit for multi-electron molecules close to spectroscopic accuracy?†

Péter G. Szalay,*^c Filip Holka,^ab Julien Fremont,^a Michael Rey,^a Kirk A. Peterson^d and Vladimir G. Tyuterev*^a

* Corresponding authors

^a Groupe de Spectrométrie Moléculaire et Atmosphérique, Reims University, Reims Cedex 2, France
E-mail: vladimir.tyuterev@univ-reims.fr
Fax: +33 326913147

^b Faculty of Materials Science and Technology, Slovak University of Technology, Paulínska 16, 917 24 Trnava, Slovak Republic

^c Institute of Chemistry, Eötvös Loránd University, Budapest, Hungary
E-mail: szalay@chem.elte.hu
Fax: +36-1-372-2592

^d Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, USA

Abstract

The aim of the study was to explore the limits of ab initio methods towards the description of excited vibrational levels up to the dissociation limit for molecules having more than two electrons. To this end a high level ab initio potential energy function was constructed for the four-electron LiH molecule in order to accurately predict a complete set of bound vibrational levels corresponding to the electronic ground state. It was composed from: (a) an ab initio non-relativistic potential obtained at the MR-CISD level including size-extensivity corrections and quintuple-sextuple ζ extrapolation of the basis, (b) MVD relativistic corrections obtained at icMR-CISD/cc-pwCV5Z level, and (c) DBOC obtained at the MR-CISD/cc-pwCVTZ level. Finally, the importance of non-adiabatic effects was also tested by using atomic masses in the vibrational kinetic energy operator. The calculated vibrational levels were compared with those obtained from experimental data [J. A. Coxon and C. S. Dickinson, J. Chem. Phys., 2004, 121, 9378]. Our best estimate of the potential curve results in vibrational energies with a RMS deviation of only ∼1 cm⁻¹ for the entire set of all empirically determined vibrational levels known so far. These results represent a drastic improvement over previous theoretical predictions of vibrational levels of ⁷LiH up to dissociation, D₀, which was predicted to be 19 594 cm⁻¹.

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DOI: https://doi.org/10.1039/C0CP01334J
Article type: Paper
Submitted: 27 Jul 2010
Accepted: 18 Nov 2010
First published: 21 Dec 2010

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Phys. Chem. Chem. Phys., 2011,13, 3654-3659

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Are ab initio quantum chemistry methods able to predict vibrational states up to the dissociation limit for multi-electron molecules close to spectroscopic accuracy?

P. G. Szalay, F. Holka, J. Fremont, M. Rey, K. A. Peterson and V. G. Tyuterev, Phys. Chem. Chem. Phys., 2011, 13, 3654 DOI: 10.1039/C0CP01334J

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Physical Chemistry Chemical Physics

Are ab initio quantum chemistry methods able to predict vibrational states up to the dissociation limit for multi-electron molecules close to spectroscopic accuracy?†

Abstract

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Are ab initio quantum chemistry methods able to predict vibrational states up to the dissociation limit for multi-electron molecules close to spectroscopic accuracy?

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