A perturbative calculation of the rovibrational energy levels of methane.
The rovibrational energy levels of methane are determined from a quartic ab initio potential energy force field where the expansion coordinates are the Morse coordinates for the stretches and extension coordinates for the bends. Energies are calculated using canonical Van Vleck perturbation theory. Results are obtained for both rotation-vibration Hamiltonians expressed as functions of curvilinear and rectilinear normal coordinates. Second, fourth, and sixth order curvilinear results are compared with experimental results, and fourth order results for the rectilinear and curvilinear Hamiltonian are compared to each other. The calculated rovibrational levels are in good agreement with the experimental values for low J levels. The calculated rotational level splittings are in even better agreement with the experiment. In particular, the ground state tetrahedral splittings, which are as small as 10(-4) cm(-1), are well reproduced by our calculations at sixth order.
Wang
Xiao-Gang
XG
Department of Chemistry and Theoretical Chemistry Institute, University of Wisconsin Madison, 53706, USA. wangx@magellan.umontreal.ca
Sibert
Edwin L
EL
D055598:Chemical Phenomena; D002627:Chemistry, Physical; D008697:Methane / Q000032:analysis / Q000737:chemistry*; D008962:Models, Theoretical; D013055:Spectrophotometry, Infrared / Q000379:methods*; D014732:Vibration
D008697:Methane