Issue 43, 2020

The role of vibronic coupling in the electronic spectroscopy of maleimide: a multi-mode and multi-state quantum dynamics study

Abstract

The first two excitation bands below 7 eV in the electronic absorption spectrum of maleimide are investigated using a model Hamiltonian including four low-lying singlet excited states within the manifold of 24 vibrational modes. The role of non-adiabatic effects is studied and shines light on both the broad, inter-state coupling–dominated spectral band as well as the fine-structured, not-so-strong coupled band. Calculations have been performed using the Multiconfigurational Time-Dependent Hartree (MCTDH) wavepacket propagation method as well as its multilayer version (ML-MCTDH) using a quadratic vibronic coupling (QVC) Hamiltonian model where parameters are obtained from fitting adiabatic potential energy surfaces computed by ab initio methods. The quantum dynamics calculations provide information on the relaxation dynamics and the vibrational modes involved. Already with a low-order vibronic coupling model and only a few modes being considered, a quantitative agreement with the experimental spectrum is obtained. However, it is found that all modes need to be considered to get a full picture of the photo-excited relaxation dynamics of this molecule.

Graphical abstract: The role of vibronic coupling in the electronic spectroscopy of maleimide: a multi-mode and multi-state quantum dynamics study

Supplementary files

Article information

Article type
Paper
Submitted
26 Aug 2020
Accepted
19 Oct 2020
First published
20 Oct 2020
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2020,22, 25272-25283

The role of vibronic coupling in the electronic spectroscopy of maleimide: a multi-mode and multi-state quantum dynamics study

A. Lehr, S. Gómez, M. A. Parkes and G. A. Worth, Phys. Chem. Chem. Phys., 2020, 22, 25272 DOI: 10.1039/D0CP04514D

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