Conical intersections in solution with polarizable embedding: Integral-exact direct reaction field

27 September 2022, Version 2
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

A common strategy to exploring the properties and reactivity of complex systems is to use quantum mechanics/molecular mechanics (QM/MM) embedding, wherein a QM region is defined and treated with electronic structure theory and the remainder of the system is treated with a force field. Important to the description of electronic excited states, especially those of charge-transfer character, is the treatment of the coupling between the QM and MM subsystems. The state-of-the-art is to use a polarizable force field for the MM region and mutually couple the QM wavefunction and MM induced dipoles, in addition to the usual electrostatic embedding, yielding a polarizable embedding (QM/MM-Pol) approach. However, we showed previously that current popular QM/MM-Pol approaches exhibit issues of root flipping and/or incorrect descriptions of electronic crossings in multistate calculations.[J. Chem. Theory Comput. 14, 2137 (2018)] Here we demonstrate a solution to these problems with an integral-exact reformulation of the Direct Reaction Field approach of Thole and Van Duijnen (QM/MM-IEDRF). The resulting embedding potential includes one- and two-electron operators, and many-body dipole-induced dipole interactions, and thus includes a natural description of the screening of electron-electron interactions by the MM induced dipoles. Pauli repulsion from the environment is mimicked by effective core potentials on the MM atoms. Inherent to the DRF approach is the assumption that MM dipoles respond instantaneously to the positions of the QM electrons, therefore dispersion interactions are captured approximately. All electronic states are eigenfunctions of the same Hamiltonian while the polarization induced in the environment and the associated energetic stabilization are unique to each state. This allows for a consistent definition of transition properties and state crossings. We demonstrate QM/MM-IEDRF by exploring the influence of a (polarizable) inert xenon matrix environment on the conical intersection underlying the photoisomerization of ethylene.

Keywords

Polarizable embedding
Conical intersections
Multiconfigurational electronic structure
Ethylene

Supplementary materials

Title
Description
Actions
Title
Supporting information
Description
Supporting figure S1
Actions
Title
Supporting information
Description
Molecular coordinates of the critical points of ethylene in an inert Xe matrix, and its derivative coupling and gradient difference vectors.
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.