Quantifying local excitation, charge resonance, and multiexciton character in correlated wave functions of multichromophoric systems

D. Casanova and A.I. Krylov
J. Chem. Phys. 144, 014102 (2016)

A new method for quantifying the contributions of local excitation, charge resonance, and multiexciton configurations in correlated wave functions of multichromophoric systems is presented. The approach relies on fragment-localized orbitals and employs spin correlators. Its utility is illustrated by calculations on model clusters of hydrogen, ethylene, and tetracene molecules using adiabatic RASCI wave functions. In addition to the wave function analysis, this approach provides a basis for a simple state-specific energy correction accounting for insufficient description of electron correlation. The decomposition scheme also allows one to compute energies of the diabatic states of the local excitonic, charge-resonance, and multi-excitonic character. The new method provides insight into electronic structure of multichromophoric systems and delivers valuable reference data for validating excitonic models.

Download this paper (PDF)

Related Research

Computational studies of electronically excited and open-shell species: Jahn-Teller systems, radicals, diradicals and triradicals