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

Author:

Taylor Jack T.1ORCID,Tozer David J.1ORCID,Curchod Basile F. E.2ORCID

Affiliation:

1. Department of Chemistry, Durham University 1 , South Road, Durham DH1 3LE, United Kingdom

2. Centre for Computational Chemistry, School of Chemistry, University of Bristol 2 , Cantock’s Close, Bristol BS8 1TS, United Kingdom

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.

Funder

Horizon 2020 Framework Programme

Engineering and Physical Sciences Research Council

Publisher

AIP Publishing

Subject

Physical and Theoretical Chemistry,General Physics and Astronomy

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