LVC/MM: A Hybrid Linear Vibronic Coupling/Molecular Mechanics Model with Distributed Multipole-Based Electrostatic Embedding for Highly Efficient Surface Hopping Dynamics in Solution

Author(s)

Severin Polonius, Oleksandra Zhuravel, Brigitta Bachmair, Sebastian Mai

Abstract

We present a theoretical framework for a hybrid linear vibronic coupling model electrostatically embedded into a molecular mechanics environment, termed the linear vibronic coupling/molecular mechanics (LVC/MM) method, for the surface hopping including arbitrary coupling (SHARC) molecular dynamics package. Electrostatic embedding is realized through the computation of interactions between environment point charges and distributed multipole expansions (DMEs, up to quadrupoles) that represent each electronic state and transition densities in the diabatic basis. The DME parameters are obtained through a restrained electrostatic potential (RESP) fit, which we extended to yield higher-order multipoles. We also implemented in SHARC a scheme for achieving roto-translational invariance of LVC models as well as a general quantum mechanics/molecular mechanics (QM/MM) interface, an OpenMM interface, and restraining potentials for simulating liquid droplets. Using thioformaldehyde in water as a test case, we demonstrate that LVC/MM can accurately reproduce the solvation structure and energetics of rigid solutes, with errors on the order of 1-2 kcal/mol compared to a BP86/MM reference. The implementation in SHARC is shown to be very efficient, enabling the simulation of trajectories on the nanosecond time scale in a matter of days.

Organisation(s)

Department of Theoretical Chemistry, Research Platform Accelerating Photoreaction Discovery

External organisation(s)

Vienna Doctoral School in Chemistry (DoSChem)

Journal

Journal of Chemical Theory and Computation

Volume

19

Pages

7171-7186

No. of pages

16

ISSN

1549-9618

DOI

https://doi.org/10.1021/acs.jctc.3c00805

Publication date

2023

Peer reviewed

Yes

Austrian Fields of Science 2012

104022 Theoretical chemistry, 102009 Computer simulation

ASJC Scopus subject areas

Computer Science Applications, Physical and Theoretical Chemistry

Portal url

https://ucrisportal.univie.ac.at/en/publications/97f3f506-7628-45be-b898-619726b70d7b