Issue 2, 2021

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

Abstract

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, the results also reveal some new insights into the origin of trends in donor–acceptor interactions.

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

Supplementary files

Article information

Article type
Paper
Submitted
10 Nov 2020
Accepted
15 Dec 2020
First published
16 Dec 2020

Phys. Chem. Chem. Phys., 2021,23, 928-943

Author version available

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

S. P. Veccham, J. Lee, Y. Mao, P. R. Horn and M. Head-Gordon, Phys. Chem. Chem. Phys., 2021, 23, 928 DOI: 10.1039/D0CP05852A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements