Characterization of quantum dynamically significant paths of bridge-mediated charge transfer systems.
In this article, we examine characteristics of quantum dynamically important paths using the on-the-fly filtered propagator functional path integral method, which evaluates a numerically accurate reduced density matrix by ignoring the vast majority of paths with insignificant contribution to the dynamics of interest. Two five-state charge-transfer systems have been considered, such that each system is governed by a different charge-transfer mechanism. It was found that, for the incoherent hopping transfer, the quantum mechanically important paths mimic classical counterparts that show little deviation between forward and backward path. Therefore, it is desirable to take advantage of a priori knowledge of the important path characteristics; in particular, it is possible to evaluate the accurate dynamics of bridge-mediated long-range charge-transfer systems efficiently in a significantly reduced quantum mechanical trajectory space.
Sim
Eunji
E
Department of Chemistry, Yonsei University, 134 Sinchondong Seodaemungu, Seoul 120-749, Korea. esim@yonsei.ac.kr
Kim
Heeyoung
H