Crossing conditions in coupled cluster theory

The Journal of Chemical Physics
Eirik F KjønstadHenrik Koch

Abstract

We derive the crossing conditions at conical intersections between electronic states in coupled cluster theory and show that if the coupled cluster Jacobian matrix is nondefective, two (three) independent conditions are correctly placed on the nuclear degrees of freedom for an inherently real (complex) Hamiltonian. Calculations using coupled cluster theory on a 21A'/31A' conical intersection in hypofluorous acid illustrate the nonphysical artifacts associated with defects at accidental same-symmetry intersections. In particular, the observed intersection seam is folded about a space of the correct dimensionality, indicating that minor modifications to the theory are required for it to provide a correct description of conical intersections in general. We find that an accidental symmetry allowed 11A″/21A″ intersection in hydrogen sulfide is properly described, showing no artifacts as well as linearity of the energy gap to first order in the branching plane.

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Sep 21, 2017·The Journal of Physical Chemistry Letters·Eirik F Kjønstad, Henrik Koch

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Citations

Apr 2, 2018·The Journal of Chemical Physics·Chenyang Li, Francesco A Evangelista
Jun 24, 2020·The Journal of Chemical Physics·Chenchen Song, Todd J Martínez
Dec 19, 2020·Journal of Chemical Theory and Computation·Eirik F Kjønstad, Henrik Koch
Nov 19, 2020·Physical Chemistry Chemical Physics : PCCP·Diego SorbelliLeonardo Belpassi
May 1, 2021·The Journal of Physical Chemistry Letters·Woojin ParkCheol Ho Choi
May 12, 2021·Journal of Computational Chemistry·Anders HutchesonIda-Marie Høyvik
Sep 6, 2019·Journal of Chemical Theory and Computation·Eirik Fadum Kjønstad, Henrik Koch
May 17, 2018·Chemical Reviews·Rachel Crespo-Otero, Mario Barbatti
Jul 25, 2018·Chemical Reviews·Hans LischkaMario Barbatti
Nov 28, 2018·The Journal of Physical Chemistry Letters·Zsuzsanna Benda, Thomas-C Jagau
Oct 1, 2021·The Journal of Physical Chemistry Letters·Woojin ParkCheol Ho Choi

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