An accurate and linear-scaling method for calculating charge-transfer excitation energies and diabatic couplings
- Department of Chemistry, Rutgers University, Newark, New Jersey 07102-1811 (United States)
- Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139-4307 (United States)
- Amsterdam Center for Multiscale Modeling, VU University, De Boelelaan 1083, 1081 HV Amsterdam (Netherlands)
- Theoretische Organische Chemie, Organisch-Chemisches Institut der Westfaelischen Wilhelms-Universitaet Muenster, Corrensstrasse 40, 48149 Muenster (Germany)
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.
- OSTI ID:
- 22105374
- Journal Information:
- Journal of Chemical Physics, Vol. 138, Issue 5; Other Information: (c) 2013 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
An energy decomposition analysis for second-order Møller–Plesset perturbation theory based on absolutely localized molecular orbitals
Determining Partial Atomic Charges for Liquid Water: Assessing Electronic Structure and Charge Models
Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACCURACY
BOND LENGTHS
CHARGE EXCHANGE
DENSITY
DENSITY FUNCTIONAL METHOD
ELECTRONIC STRUCTURE
ELECTRONS
EXCITATION
EXCITED STATES
HAMILTONIANS
HYDROGEN
MOLECULAR CLUSTERS
MOLECULES
QUANTUM MECHANICS
REACTION KINETICS