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arXiv · 1404.0487

Global potential energy surface for the O2 + N2 interaction. Applications to the collisional, spectroscopic, and thermodynamic properties of the complex

Massimiliano Bartolomei·Estela Carmona-Novillo·Marta I. Hernádez·José Campos-Martínez·Robert Moszyński
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Abstract

A detailed characterization of the interaction between the most abundant molecules in air is important for the understanding of a variety of phenomena in atmospherical science. A completely {\em ab initio} global potential energy surface (PES) for the O$_2(^3Σ^-_g)$ + N$_2(^1Σ^+_g)$ interaction is reported for the first time. It has been obtained with the symmetry-adapted perturbation theory utilizing a density functional description of monomers [SAPT(DFT)] extended to treat the interaction involving high-spin open-shell complexes. The computed interaction energies of the complex are in a good agreement with those obtained by using the spin-restricted coupled cluster methodology with singles, doubles and noniterative triple excitations [RCCSD(T)]. A spherical harmonics expansion containing a large number of terms due to the anisotropy of the interaction has been built from the {\em ab initio} data. The radial coefficients of the expansion are matched in the long range with the analytical functions based on the recent {\em ab initio} calculations of the electric properties of the monomers [M. Bartolomei et al., J. Comp. Chem., {\bf 32}, 279 (2011)]. The PES is tested against the second virial coefficient $B(T)$ data and the integral cross sections measured with rotationally hot effusive beams, leading in both cases to a very good agreement. The first bound states of the complex have been computed and relevant spectroscopic features of the interacting complex are reported. A comparison with a previous experimentally derived PES is also provided.

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Massimiliano Bartolomei, Estela Carmona-Novillo, Marta I. Hernádez, José Campos-Martínez, Robert Moszyński. 2014-04-02. Global potential energy surface for the O2 + N2 interaction. Applications to the collisional, spectroscopic, and thermodynamic properties of the complex. https://doi.org/10.1021/jp503182h

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