Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 138, Issue 5, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.4789418
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Funding
- Department of Chemistry
- office of the Dean of FASN, Rutgers-Newark
- Netherlands Organization for Scientific Research (NWO) [700.59.422]
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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 Angstroms. Numerical examples are provided for molecular clusters comprised of up to 56 non-covalently bound molecules. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4789418]
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