A comparison of spin-flip TDDFT-based conical intersection approaches with XMS-CASPT2

Winslow, M., Cross, W.B. ORCID: 0000-0001-6277-400X and Robinson, D. ORCID: 0000-0003-2760-7163, 2020. A comparison of spin-flip TDDFT-based conical intersection approaches with XMS-CASPT2. Journal of Chemical Theory and Computation, 16 (5), pp. 3253-3263. ISSN 1549-9618

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Determining conical intersection geometries is of key importance to understanding the photochemical reactivity of molecules. While many small to medium-sized molecules can be treated accurately using multireference approaches, larger molecules require a less computationally demanding approach. In this work, minimum energy crossing point conical intersection geometries for a series of molecules has been studied using spin-flip TDDFT (SF-TDDFT), within the Tamm-Dancoff Approximaton, both with and without explicit calculation of non-adiabatic coupling terms, and compared with both XMS-CASPT2 and CASSCF calculated geometries. The less-computationally demanding algorithms, which do not require explicit calculation of the non-adiabatic coupling terms, generally fare well with the XMS-CASPT2 reference structures, while the relative energetics are only reasonably replicated with the MECP structure calculated with the BHHLYP functional and full non-adiabatic coupling terms. We also demonstrate that, occasionally, CASSCF structures deviate quantitatively from the XMS-CASPT2 structures, showing the importance of including dynamical correlation.

Item Type: Journal article
Publication Title: Journal of Chemical Theory and Computation
Creators: Winslow, M., Cross, W.B. and Robinson, D.
Publisher: American Chemical Society
Date: 12 May 2020
Volume: 16
Number: 5
ISSN: 1549-9618
Divisions: Schools > School of Science and Technology
Record created by: Linda Sullivan
Date Added: 22 Apr 2020 10:16
Last Modified: 31 May 2021 15:04
URI: https://irep.ntu.ac.uk/id/eprint/39716

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