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Correlated intermolecular interaction components from asymptotically corrected Kohn-Sham orbitals

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Abstract

The symmetry-adapted perturbation theory (SAPT) that has the ability in decomposition of the total interaction energy into physically meaningful components is used to provide a more fundamental understanding of intermolecular forces. This work was motivated by the difficulty of standard SAPT in computing the intermolecular interactions for large energetic dimer systems. SAPT based on Kohn-Sham orbitals (SAPT(DFT)) proves computationally efficient for these large systems, but has been shown to perform poorly for interaction energy components. The deficiencies of SAPT(DFT) result from wrong asymptotical behaviors of commonly used exchange-correlation potentials. To remove the deficiencies, two asymptotic corrections by means of van Leeuwen and Baerends (LB) model potential and Fermi-Amaldi (FA) type potential were applied into three small test systems comprising He2, HF2 and (N2)2 and a set of larger nitramide dimers at several separations. The results showed that when utilizing newly developed frequency-dependent density susceptibilities (FDDS) technique for computing dispersion energy, the FA asymptotic correction is very effective to circumvent these deficiencies in SAPT(DFT) and yields a good accuracy over the LB correction. The FA corrected SAPT(DFT) approach is capable of correctly predicting all the quantitative trends in binding energies for all test cases and substantially reduces computational cost as compared with the standard SAPT calculations. The successful application of the approach to nitramide dimer demonstrates that it potentially provides a good means to calculate accurately intermolecular forces in larger system such as energetic systems.

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Authors and Affiliations

  1. Department of Chemistry, Nanjing University of Science and Technology, 210094, Nanjing, China

    Huajie Song & Heming Xiao

  2. Institute of Chemical Materials, China Academy of Engineering Physics, 621900, Mianyang, China

    Huajie Song & Haishan Dong

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  1. Huajie Song
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  2. Heming Xiao
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Correspondence to Huajie Song.

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Song, H., Xiao, H. & Dong, H. Correlated intermolecular interaction components from asymptotically corrected Kohn-Sham orbitals. Sc. China Ser. B-Chem. 47, 466–479 (2004). https://doi.org/10.1360/04yb0078

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