Excited state geometry optimization with the density matrix renormalization group as applied to polyenes
Chemical Physics
2015-03-03 v2
Abstract
We describe and extend the formalism of state-specific analytic density matrix renormalization group (DMRG) energy gradients, first used by Liu et al (J. Chem. Theor.Comput. 9, 4462 (2013)). We introduce a DMRG wavefunction maximum overlap following technique to facilitate state-specific DMRG excited state optimization. Using DMRG configuration interaction (DMRG-CI) gradients we relax the low-lying singlet states of a series of trans-polyenes up to C20H22. Using the relaxed excited state geometries as well as correlation functions, we elucidate the exciton, soliton, and bimagnon ("single-fission") character of the excited states, and find evidence for a planar conical intersection.
Cite
@article{arxiv.1502.07731,
title = {Excited state geometry optimization with the density matrix renormalization group as applied to polyenes},
author = {Weifeng Hu and Garnet Kin-Lic Chan},
journal= {arXiv preprint arXiv:1502.07731},
year = {2015}
}