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On the description of conical intersections between excited electronic states with LR-TDDFT and ADC(2).

Taylor, Jack T; Tozer, David J; Curchod, Basile F E

On the description of conical intersections between excited electronic states with LR-TDDFT and ADC(2). Thumbnail


Authors

Jack Taylor jack.taylor@durham.ac.uk
PGR Student Doctor of Philosophy



Abstract

Conical intersections constitute the conceptual bedrock of our working understanding of ultrafast, nonadiabatic processes within photochemistry (and photophysics). Accurate calculation of potential energy surfaces within the vicinity of conical intersections, however, still poses a serious challenge to many popular electronic structure methods. Multiple works have reported on the deficiency of methods like linear-response time-dependent density functional theory within the adiabatic approximation (AA LR-TDDFT) or algebraic diagrammatic construction to second-order [ADC(2)]-approaches often used in excited-state molecular dynamics simulations-to describe conical intersections between the ground and excited electronic states. In the present study, we focus our attention on conical intersections between excited electronic states and probe the ability of AA LR-TDDFT and ADC(2) to describe their topology and topography, using protonated formaldimine and pyrazine as two exemplar molecules. We also take the opportunity to revisit the performance of these methods in describing conical intersections involving the ground electronic state in protonated formaldimine-highlighting in particular how the intersection ring exhibited by AA LR-TDDFT can be perceived either as a (near-to-linear) seam of intersection or two interpenetrating cones, depending on the magnitude of molecular distortions within the branching space. [Abstract copyright: © 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).]

Citation

Taylor, J. T., Tozer, D. J., & Curchod, B. F. E. (2023). On the description of conical intersections between excited electronic states with LR-TDDFT and ADC(2). The Journal of Chemical Physics, 159(21), Article 214115. https://doi.org/10.1063/5.0176140

Journal Article Type Article
Acceptance Date Nov 14, 2023
Online Publication Date Dec 7, 2023
Publication Date Dec 7, 2023
Deposit Date Jan 4, 2024
Publicly Available Date Jan 4, 2024
Journal The Journal of chemical physics
Print ISSN 0021-9606
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 159
Issue 21
Article Number 214115
DOI https://doi.org/10.1063/5.0176140
Public URL https://durham-repository.worktribe.com/output/2049794

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