Improving the calculation of rovibrational spectra of five-atom molecules with three identical atoms by using a C3upsilonG6 symmetry-adapted grid: applied to CH3D and CHD3.
In this paper we report two improvements on the approach we have used to compute rovibrational levels of methane and apply the new ideas to calculate rovibrational levels of two methane isotopomers CH3D and CHD3. Both improvements make the bend calculation better. The first improvement is a G6-invariant (or C3upsilon-invariant) grid which is designed such that each point on the grid is mapped to another point on the grid by any of the G6 operations. The second improvement is the use of fast Fourier transform (FFT) to compute the bend potential matrix-vector products. The FFT matrix-vector product is about three and ten times faster than the previous sequential summation method for the J=0 and J>0 cases, respectively. The calculated J=1 rovibrational levels of CH3D and CHD3 on the Schwenke and Partridge [Spectrochim. Acta, Part A 57, 887 (2001)] ab initio potential are in good agreement (within 6 cm(-1) for the levels up to 3000 cm(-1)) with the experimental data. The agreement is even better (within 0.1 cm(-1) for the levels up to 6000 cm(-1)) if the associated J=0 energies are subtracted.
Wang
Xiao-Gang
XG
Départment de chimie, Université de Montréal, CP 6128, succursale Centre-ville, Montréal (Québec) H3C 3J7, Canada. Xiaogang.Wang@umontreal.ca
Carrington
Tucker
T