Nitrous oxide dimer: A new potential energy surface and rovibrational spectrum of the nonpolar isomer

Richard Dawes, Xiao-Gang Wang, Ahren W. Jasper, Tucker Carrington
2010 Journal of Chemical Physics  
The spectrum of nitrous oxide dimer was investigated by constructing new potential energy surfaces using coupled-cluster theory and solving the rovibrational Schrödinger equation with a Lanczos algorithm. Two four-dimensional ͑rigid monomer͒ global ab initio potential energy surfaces ͑PESs͒ were made using an interpolating moving least-squares ͑IMLS͒ fitting procedure specialized to describe the interaction of two linear fragments. The first exploratory fit was made from 1646 CCSD͑T͒/3ZaP
more » ... CCSD͑T͒/3ZaP energies. Isomeric minima and connecting transition structures were located on the fitted surface, and the energies of those geometries were benchmarked using complete basis set ͑CBS͒ extrapolations, counterpoise ͑CP͒ corrections, and explicitly correlated ͑F12b͒ methods. At the geometries tested, the explicitly correlated F12b method produced energies in close agreement with the estimated CBS limit. A second fit to 1757 data at the CCSD͑T͒-F12b/VTZ-F12 level was constructed with an estimated fitting error of less than 1.5 cm −1 . The second surface has a global nonpolar O-in minimum, two T-shaped N-in minima, and two polar minima. Barriers between these minima are small and some wave functions have amplitudes in several wells. Low-lying rovibrational wave functions and energy levels up to about 150 cm −1 were computed on the F12b PES using a discrete variable representation/finite basis representation method. Calculated rotational constants and intermolecular frequencies are in very close agreement with experiment.
doi:10.1063/1.3494542 pmid:20942536 fatcat:m5ibjlo5gfd3dij6iu7yqr6h2u