A non-perturbative pairwise-additive analysis of charge transfer contributions to intermolecular interaction energies

Veccham, Srimukh Prasad; Lee, Joonho; Mao, Yuezhi; Horn, Paul R.; Head-Gordon, Martin

doi:10.1039/d0cp05852a

Title: A non-perturbative pairwise-additive analysis of charge transfer contributions to intermolecular interaction energies

Journal Article · Wed Dec 16 00:00:00 EST 2020 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d0cp05852a· OSTI ID:1779266

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Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Columbia Univ., New York, NY (United States)

Energy decomposition analysis (EDA) based on absolutely localized molecular orbitals (ALMOs) decomposes the interaction energy between molecules into physically interpretable components like geometry distortion, frozen interactions, polarization, and charge transfer (CT, also sometimes called charge delocalization) interactions. In this work, a numerically exact scheme to decompose the CT interaction energy into pairwise additive terms is introduced for the ALMO-EDA using density functional theory. Unlike perturbative pairwise charge-decomposition analysis, the new approach does not break down for strongly interacting systems, or show significant exchange–correlation functional dependence in the decomposed energy components. Both the energy lowering and the charge flow associated with CT can be decomposed. Complementary occupied–virtual orbital pairs (COVPs) that capture the dominant donor and acceptor CT orbitals are obtained for the new decomposition. It is applied to systems with different types of interactions including DNA base-pairs, borane-ammonia adducts, and transition metal hexacarbonyls. While consistent with most existing understanding of the nature of CT in these systems, we report the results also reveal some new insights into the origin of trends in donor–acceptor interactions.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC02-05CH11231; CHE-1955643

OSTI ID:: 1779266

Alternate ID(s):: OSTI ID: 1742055

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 23, Issue 2; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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