Potential-energy surface for the electronic ground state of N H3 up to 20 000 cm -1 above equilibrium

Sergei N. Yurchenko, Jingjing Zheng, Hai Lin, Per Jensen, Walter Thiel

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Abstract

Ab initio coupled cluster calculations with single and double substitutions and a perturbative treatment of connected triple excitations [CCSD(T)] with the augmented correlation-consistent polarized valence triple-zeta aug-cc-pVTZ basis at 51 816 geometries provide a six-dimensional potential-energy surface for the electronic ground state of N H3. At 3814 selected geometries, CBS + energies are obtained by extrapolating the CCSD(T) results for the aug-cc-pVXZ (X=T,Q,5) basis sets to the complete basis set (CBS) limit and adding corrections for core-valence correlation and relativistic effects. CBS* ab initio energies are generated at 51 816 geometries by an empirical extrapolation of the CCSD(T)/aug-cc-pVTZ results to the CBS+ limit. They cover the energy region up to 20 000 cm-1 above equilibrium. Parametrized analytical functions are fitted through the ab initio points. For these analytical surfaces, vibrational term values and transition moments are calculated by means of a variational program employing a kinetic-energy operator expressed in the Eckart-Sayvetz frame. Comparisons against experiment are used to assess the quality of the generated potential-energy surfaces. A "spectroscopic" potential-energy surface of N H3 is determined by a slight empirical adjustment of the ab initio potential to the experimental vibrational term values. Variational calculations on this refined surface yield rms deviations from experiment of 0.8 cm-1 for 24 inversion splittings and 0.4 (3.0) cm-1 for 34 (51) vibrational term values up to 6100 (10 300) cm-1.

Original languageEnglish (US)
Article number134308
JournalJournal of Chemical Physics
Volume123
Issue number13
DOIs
StatePublished - Oct 3 2005

Bibliographical note

Funding Information:
This work was supported by the European Commission through Contract No. HPRN-CT-2000-00022, “Spectroscopy of Highly Excited Rovibrational States,” and Contract No. MRTN-CT-2004-512202, “Quantitative Spectroscopy for Atmospheric and Astrophysical Research.” The work of one of the authors (P.J.) is supported in part by the Deutsche Forschungsgemeinschaft and the Fonds der chemischen Industrie.

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