Ab initio potential energy surface and intermolecular vibrations of the naphthalene-argon van der Waals complex.

The intermolecular potential energy surface (PES) of the naphthalene-argon (NpAr) complex is constructed using an ab initio method. The molecule-argon interaction energy is computed at the level of the second-order Møller-Plesset (MP2) theory combined with the augmented correlation consistent polarized valence double-ζ basis set. The analytical PES fitted to a large set of single energy values is further improved with the help of correction functions determined by calculations of the interaction energy at the coupled cluster level including single and double excitations supplemented by triple excitations performed for a limited set of intermolecular configurations. The PES determined is very flat near its four equivalent global minima of -493 cm(-1) located from both sides of the Np plane at a distance of 3.435 Å and shifted from the center of Np by ±0.43 Å along its long symmetry axis. The large-amplitude motion of Ar in the complex is investigated, and dynamical consequence of a strong intermode coupling is discovered in the excited vibrational states. The theoretical results obtained allow for the reassignment of the spectral bands observed in the electronic transition S(1) ← S(0) of the NpAr complex.

Citation

Jan Makarewicz. Ab initio potential energy surface and intermolecular vibrations of the naphthalene-argon van der Waals complex. The Journal of chemical physics. 2011 Feb 14;134(6):064322

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PMID: 21322695

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