An accurate and linear-scaling method for calculating charge-transfer excitation energies and diabatic couplings
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Author(s)
Pavanello, Michele
Van Voorhis, Troy
Visscher, Lucas
Neugebauer, Johannes
Date Issued
February 2013
Journal
The Journal of Chemical Physics
Publisher
American Institute of Physics (AIP)
Citation
Pavanello, Michele, Troy Van Voorhis, Lucas Visscher, and Johannes Neugebauer. “An accurate and linear-scaling method for calculating charge-transfer excitation energies and diabatic couplings.” The Journal of Chemical Physics 138, no. 5 (2013): 054101. © 2013 American Institute of Physics
Version
Final published version
Abstract
Quantum–mechanical methods that are both computationally fast and accurate are not yet available for electronic excitations having charge transfer character. In this work, we present a significant step forward towards this goal for those charge transfer excitations that take place between non-covalently bound molecules. In particular, we present a method that scales linearly with the number of non-covalently bound molecules in the system and is based on a two-pronged approach: The molecular electronic structure of broken-symmetry charge-localized states is obtained with the frozen density embedding formulation of subsystem density-functional theory; subsequently, in a post-SCF calculation, the full-electron Hamiltonian and overlap matrix elements among the charge-localized states are evaluated with an algorithm which takes full advantage of the subsystem DFT density partitioning technique. The method is benchmarked against coupled-cluster calculations and achieves chemical accuracy for the systems considered for intermolecular separations ranging from hydrogen-bond distances to tens of Ångstroms. Numerical examples are provided for molecular clusters comprised of up to 56 non-covalently bound molecules.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
https://doi.org/10.1063/1.4789418
