Nitrous Oxide Dimer: A New Potential Energy Surface and Rovibrational Spectrum of the Nonpolar Isomer


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 monomer) global ab initio potential energy surfaces (PESs) were made using an interpolating moving least-squares (IMLS) fitting procedure specialized to describe the interaction of two linear fragments. The first exploratory fit was made from 1646 CCSD(T)/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 (CBS) extrapolations, counterpoise (CP) corrections, and explicitly correlated (F12b) 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 CCSD(T)-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



Keywords and Phrases

Ab initio potential energy surface; CCSD; Complete basis sets; Coupled-cluster theory; Dinger equation; Discrete variables; Energy level; Fitting error; Fitting procedure; Lanczos algorithm; Linear fragments; Moving least squares; Nitrous oxide; Non-polar; Nonpolar isomers; Representation method; Rotational constants; Rovibrational spectrum; Transition structures; Anesthetics; Dimers; Electric circuit breakers; Nitrogen oxides; Potential energy; Potential energy surfaces; Surface phenomena; Wave functions; Quantum chemistry

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