BSE@GW-based protocol for spin-vibronic quantum dynamics using the linear vibronic coupling model. Formulation and application to an Fe(ii) compound

Author(s)

Florian Bogdain, Sebastian Mai, Leticia González, Oliver Kühn

Abstract

A protocol for generating potential energy surfaces and performing photoinduced nonadiabatic multidimensional wave packet propagation is presented. The workflow starts with the parameterization of a linear vibronic coupling (LVC) Hamiltonian using the Green's function - Bethe-Salpeter equation (BSE@GW) approach. In a second step, the LVC model is used as input for multi-layer multi-configurational time-dependent Hartree (ML-MCTDH) wave packet propagation. To facilitate automated ML tree generation, a spectral clustering algorithm is applied based on a correlation matrix obtained from nuclear coordinate expectation values of a full-dimensional time-dependent Hartree (TDH) simulation. The performance of the protocol is tested on the photoinduced spin-vibronic dynamics of a transition metal complex, [Fe(cpmp)]²⁺. For this example, it is shown that BSE@GW provides a more robust description of the character of the transitions contributing to the absorption spectrum compared to TD-DFT. Furthermore, the LVC parameterization is tested against explicit calculations of potential energy curves to find the validity of the linear approximation over a wide range of normal mode elongation. Finally, the flexibility of spectral clustering is used to generate different ML trees, resulting in very different numerical efficiencies for ML-MCTDH propagation. In terms of electronic structure and dimensionality, [Fe(cpmp)]²⁺ is a challenging example, suggesting that the new protocol should be applicable to a wide range of systems.

Organisation(s)

Department of Theoretical Chemistry, Research Platform Accelerating Photoreaction Discovery

External organisation(s)

Universität Rostock

Journal

Physical Chemistry Chemical Physics

Volume

27

Pages

15609-15621

No. of pages

13

ISSN

1463-9076

DOI

https://doi.org/10.1039/d5cp01208b

Publication date

07-2025

Peer reviewed

Yes

Austrian Fields of Science 2012

103006 Chemical physics, 104017 Physical chemistry

ASJC Scopus subject areas

General Physics and Astronomy, Physical and Theoretical Chemistry

Portal url

https://ucrisportal.univie.ac.at/en/publications/7240abbe-a430-484c-a4b0-20cabb478554