Distributed Multipolar Expansion Approach to Calculation
of Excitation Energy Transfer Couplings
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Abstract
We
propose a new approach for estimating the electrostatic part
of the excitation energy transfer (EET) coupling between electronically
excited chromophores based on the transition density-derived cumulative
atomic multipole moments (TrCAMM). In this approach, the transition
potential of a chromophore is expressed in terms of truncated distributed
multipolar expansion and analytical formulas for the TrCAMMs are derived.
The accuracy and computational feasibility of the proposed approach
is tested against the exact Coulombic couplings, and various multipole
expansion truncation schemes are analyzed. The results of preliminary
calculations show that the TrCAMM approach is capable of reproducing
the exact Coulombic EET couplings accurately and efficiently and is
superior to other widely used schemes: the transition charges from
electrostatic potential (TrESP) and the transition density cube (TDC)
method