Article,
A general ansatz for constructing quasi-diabatic states in electronically excited aggregated systems
J. Chem. Phys., 143 (8): 084106-- (August 2015)
DOI: 10.1063/1.4929352
Abstract
We present a general method for analyzing the character of singly excited states in terms of charge transfer (CT) and locally excited (LE) configurations. The analysis is formulated for configuration interaction singles (CIS) singly excited wave functions of aggregate systems. It also approximately works for the second-order approximate coupled cluster singles and doubles and the second-order algebraic-diagrammatic construction methods CC2 and ADC(2). The analysis method not only generates a weight of each character for an excited state, but also allows to define the related quasi-diabatic states and corresponding coupling matrix elements. In the character analysis approach, we divide the target system into domains and use a modified Pipek-Mezey algorithm to localize the canonical MOs on each domain, respectively. The CIS wavefunction is then transformed into the localized basis, which allows us to partition the wavefunction into LE configurations within domains and CT configuration between pairs of dif...
