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Published July 14, 2015 | Published + Submitted + Supplemental Material
Journal Article Open

Excited-State Geometry Optimization with the Density Matrix Renormalization Group, as Applied to Polyenes


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. 2013, 9, 4462]. We introduce a DMRG wave function 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.

Additional Information

© 2015 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: February 22, 2015. Published: May 14, 2015. W.H. thanks Gerald Knizia and Bo-Xiao Zheng, for discussions on the gradient theory, and Sandeep Sharma, for help with the BLOCK DMRG code. This work was supported by the U.S. National Science Foundation (Nos. CHE-1265277 and CHE-1265278). The authors declare no competing financial interest.

Attached Files

Submitted - 1502.07731.pdf

Supplemental Material - acs_Ejctc_E5b00174.pdf

Published - ct5b00174_si_001.pdf


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August 20, 2023
August 20, 2023