Fitting potential energy and induced dipole surfaces of the van der Waals complex CH4–N2 using non-product quadrature grids†
Abstract
We present an extensive study of the five-dimensional potential energy and induced dipole surfaces of the CH4–N2 complex assuming rigid-rotor approximation. Within the supermolecular approach, ab initio calculations of the interaction energies and dipoles were carried out at the CCSD(T)-F12 and CCSD(T) levels of theory using the correlation-consistent aug-cc-pVTZ basis set, respectively. Both potential energy and induced dipole surfaces inherit the symmetry of the molecular system and transform under the A1+ and A2+ irreducible representations of the molecular symmetry group G48, respectively. One can take advantage of the symmetry when fitting the surfaces; first, when constructing angular basis functions and second, when selecting the grid points. The approach to the construction of scalar and vectorial basis functions exploiting the eigenfunction method [Q. Chen, J. Ping and F. Wang, Group Representation Theory for Physicists, World Scientific, 2nd edn, 2002] is developed. We explore the use of Sobolev-type quadrature grids as building blocks of robust quadrature rules adapted to the symmetry of the molecular system. Temperature variations of the cross second virial coefficient and first classical spectral moments of the rototranslational collision-induced band were derived. A reasonable agreement between calculated values and experimental data was found attesting to the high quality of constructed surfaces.
- This article is part of the themed collection: 2021 PCCP HOT Articles
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