Rovibrational dynamics of RbCs on its lowest (1,3)Σ+ potential curves calculated by coupled cluster method with all-electron basis set

J Phys Chem A. 2012 Nov 26;116(46):11101-6. doi: 10.1021/jp303975x. Epub 2012 Aug 22.

Abstract

Relativistic ab initio potential curves of RbCs lowest (1,3)Σ(+) states are calculated by diagonalizing the Douglas-Kroll-Hess Hamiltonian as implemented in Gaussian09 suite of programs. The ab initio calculations are performed at the CCSD(T) level with UGBS1P+ basis set, a huge all-electron basis set. The rovibrational eigenenergies and eigenfunctions on the lowest (1,3)Σ(+) ab initio potential curves are calculated by direct diagonalization of molecular Hamiltonian in a Fourier grid discrete variable representation. The results agree well with available experimental and theoretical work and the accuracy of theoretical descriptions of RbCs are increased, which is expected to be a good reference for further investigations.