We present the extension of Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) to real-time Time Dependent Density Functional Theory (rt-TDDFT). FDE is a DFT-in-DFT embedding method that allows to partition a larger Kohn-Sham system into a set of smaller, coupled Kohn-Sham systems. Additional to the computational advantage, FDE provides physical insight into the properties of embedded systems and the coupling interactions between them. The extension to rt-TDDFT is done straightforwardly by evolving the Kohn-Sham subsystems in time simultaneously, while updating the embedding potential between the systems at every time step. Two main applications are presented: the explicit excitation energy transfer in real time between subsystems is demonstrated for the case of the Na4 cluster and the effect of the embedding on optical spectra of coupled chromophores. In particular, the importance of including the full dynamic response in the embedding potential is demonstrated.
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21 April 2015
Research Article|
April 20 2015
Subsystem real-time time dependent density functional theory
Alisa Krishtal
;
Alisa Krishtal
1Department of Chemistry,
Rutgers University
, Newark, New Jersey 07102, USA
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Davide Ceresoli
;
Davide Ceresoli
1Department of Chemistry,
Rutgers University
, Newark, New Jersey 07102, USA
2
CNR-ISTM, Institute of Molecular Sciences and Technologies
, Milan, Italy
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Michele Pavanello
Michele Pavanello
a)
1Department of Chemistry,
Rutgers University
, Newark, New Jersey 07102, USA
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a)
Author to whom correspondence should be addressed. Electronic mail: [email protected]
J. Chem. Phys. 142, 154116 (2015)
Article history
Received:
January 19 2015
Accepted:
April 03 2015
Citation
Alisa Krishtal, Davide Ceresoli, Michele Pavanello; Subsystem real-time time dependent density functional theory. J. Chem. Phys. 21 April 2015; 142 (15): 154116. https://doi.org/10.1063/1.4918276
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