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Vibrational spectrum of BiH3: Six-dimensional variational calculations on high-level ab initio potential energy surfaces

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Abstract

We report a theoretical study of the ground electronic state of BiH3. The potential energy surface (PES) is obtained from coupled cluster CCSD(T) calculations with a large basis set (289 contracted Gaussian functions). The previously available quartic force field (P4) is extended by adding the dominant quintic and sextic stretching terms to yield improved potential functions in symmetry coordinates (P6) and Morse-type coordinates (M4). Second-order rovibrational perturbation calculations on the P4-PES and full variational calculations on the P6-PES and M4-PES yield almost identical vibrational term values which is rationalized by considering the local mode behavior of BiH3 and the Morse-type character of the M4-PES. The remaining deviations between the computed and observed vibrational term values must thus be caused by imperfections in the CCSD(T) surface. A refinement of this ab initio surface by a restrained fit to experimental data allows an essentially perfect reproduction of the observed vibrational term values. Variational calculations on this refined surface provide predictions for several overtone and combination bands that have not yet been observed.

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Authors and Affiliations

  1. Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany

    Sergei N. Yurchenko, Jürgen Breidung & Walter Thiel

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  1. Sergei N. Yurchenko
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  2. Jürgen Breidung
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  3. Walter Thiel
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Correspondence to Walter Thiel.

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Dedicated to Hermann Stoll on the occasion of his 60th birthday

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Yurchenko, S., Breidung, J. & Thiel, W. Vibrational spectrum of BiH3: Six-dimensional variational calculations on high-level ab initio potential energy surfaces. Theor Chem Acc 114, 333–340 (2005). https://doi.org/10.1007/s00214-005-0687-3

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  • DOI: https://doi.org/10.1007/s00214-005-0687-3

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