Published in

American Institute of Physics, The Journal of Chemical Physics, 24(117), p. 11265

DOI: 10.1063/1.1521762

Links

Tools

Export citation

Search in Google Scholar

Vibrational energies for NH3 based on high level ab initio potential energy surfaces

Journal article published in 2002 by Hai Lin, Walter Thiel ORCID, Sergei N. Yurchenko ORCID, Miguel Carvajal, Per Jensen
This paper is available in a repository.
This paper is available in a repository.

Full text: Download

Green circle
Preprint: archiving allowed
Green circle
Postprint: archiving allowed
Orange circle
Published version: archiving restricted
Data provided by SHERPA/RoMEO

Abstract

Ab initio coupled cluster calculations with single and double substitutions and a perturbative treatment of connected triple substitutions [CCSD(T)] have been carried out to generate six- dimensional (6D) potential energy surfaces (PES) and dipole moment surfaces (DMS) for the electronic ground state of ammonia. Full 6D-PES and 6D-DMS (14400 points) were computed with the augmented correlation-consistent triple-zeta basis (aug-cc-pVTZ). For a selected number of points (420 in C-3v symmetry and 1260 in lower symmetry), more accurate energies (CBS+) were obtained by extrapolating the CCSD(T) results for the aug-cc-pVXZ (X=T,Q,5) basis sets to the complete basis set limit and adding corrections for core-valence correlation and relativistic effects. Two procedures were investigated to enhance the quality of the 6D-PES from CCSD(T)/aug-cc-pVTZ by including the CBS+ data points. The resulting 6D-PES were represented by analytical functions involving Morse variables for the stretches, symmetry-adapted bending coordinates, and a specially designed inversion coordinate (up to 76 fitted parameters, rms deviations of about 5 cm(-1) for 14 400 ab initio data points). For these analytical surfaces, vibrational energies were calculated with a newly developed computer program using a variational model that employs an Eckart-frame kinetic energy operator. Results are presented and compared to experiment for the vibrational band centers of NH3 and its isotopomers up to around 15 000 cm(-1). For our best 6D-PES, the term values of the fundamentals are reproduced with rms deviations of 4.4 cm(-1) (NH3) and 2.6 cm(-1) (all isotopomers), the maximum deviation being 7.9 cm(-1). (C) 2002 American Institute of Physics.