Molecule-Environment Embedding with Quantum Monte Carlo: Electrons Interacting with Drude Oscillators.

[en] We present a comprehensive investigation of the El-QDO embedding method [Phys. Rev. Lett. 131, 228001 (2023)], where molecular systems described through the electronic Hamiltonian are immersed in a bath of charged quantum harmonic oscillators, i.e., quantum Drude oscillators (QDOs). In the El-QDO model, the entire system of electrons and drudons─the quantum particles in the QDOs─is modeled through a single Hamiltonian which is solved through quantum Monte Carlo (QMC) methods. We first describe the details of the El-QDO Hamiltonian, of the proposed El-QDO ansatz, and of the QMC algorithms implemented to integrate both electronic and drudonic degrees of freedom. Then we analyze short-range regularization functions for the interacting potential between electrons and QDOs in order to accurately treat equilibrium and repulsive regions, resolving the overpolarization error that occurs between the electronic system and the environment. After benchmarking various regularization (damping) functions on the cases of argon and water dimers, the El-QDO method is applied to study the solvation energies of the benzene and water dimers, verifying the accuracy of the El-QDO approach compared to accurate fully electronic ab initio calculations. Furthermore, through the comparison of the El-QDO interaction energies with the components of Symmetry-Adapted Perturbation Theory calculations, we illustrate the El-QDO's explicit many-body treatment of electrostatic, polarization, and dispersion interactions between the electronic subsystem and the environment.

Research center :

ULHPC - University of Luxembourg: High Performance Computing

Precision for document type :

Review article

Disciplines :

Physics

Author, co-author :

DITTE, Matej ; University of Luxembourg

BARBORINI, Matteo ; University of Luxembourg

TKATCHENKO, Alexandre ; University of Luxembourg > Faculty of Science, Technology and Medicine (FSTM) > Department of Physics and Materials Science (DPHYMS)

External co-authors :

Language :

English

Title :

Molecule-Environment Embedding with Quantum Monte Carlo: Electrons Interacting with Drude Oscillators.

Publication date :

30 April 2025

Journal title :

Journal of Chemical Theory and Computation

ISSN :

1549-9618

eISSN :

1549-9626

Publisher :

American Chemical Society (ACS), United States

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

https://pubs.acs.org/doi/pdf/10.1021/acs.jctc.5c00108

European Projects :

HE - 101054629 - FITMOL - Field-Theory Approach to Molecular Interactions

FnR Project :

FNR18093472 - MBD-in-BMD - Many-body Dispersion Interactions In Bio-molecular Dynamics, 2023 (01/09/2024-31/08/2027) - Alexandre Tkatchenko

Funders :

European Research Council
Fonds National de la Recherche Luxembourg
European Union

Available on ORBilu :

since 02 May 2025

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