Influence of non-adiabatic effects on linear absorption spectra in the condensed phase: Methylene blue - Sorbonne Université
Article Dans Une Revue The Journal of Chemical Physics Année : 2021

Influence of non-adiabatic effects on linear absorption spectra in the condensed phase: Methylene blue

Angus J Dunnett
  • Fonction : Auteur
Duncan Gowland
  • Fonction : Auteur
Christine M Isborn
  • Fonction : Auteur
Alex W. Chin
Tim J Zuehlsdorff
  • Fonction : Auteur

Résumé

Modeling linear absorption spectra of solvated chromophores is highly challenging as contributions are present both from coupling of the electronic states to nuclear vibrations and solute-solvent interactions. In systems where excited states intersect in the Condon region, significant non-adiabatic contributions to absorption lineshapes can also be observed. Here, we introduce a robust approach to model linear absorption spectra accounting for both environmental and non-adiabatic effects from first principles. This model parameterizes a linear vibronic coupling (LVC) Hamiltonian directly from energy gap fluctuations calculated along molecular dynamics (MD) trajectories of the chromophore in solution, accounting for both anharmonicity in the potential and direct solute-solvent interactions. The resulting system dynamics described by the LVC Hamiltonian are solved exactly using the thermalized time-evolving density operator with orthogonal polynomials algorithm (T-TEDOPA). The approach is applied to the linear absorption spectrum of methylene blue (MB) in water. We show that the strong shoulder in the experimental spectrum is caused by vibrationally driven population transfer between the bright S 1 and the dark S 2 state. The treatment of the solvent environment is one of many factors which strongly influences the population transfer and lineshape; accurate modeling can only be achieved through the use of explicit quantum mechanical solvation. The efficiency of T-TEDOPA, combined with LVC Hamiltonian parameterizations from MD, leads to an attractive method for describing a large variety of systems in complex environments from first principles.
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Dates et versions

hal-03423096 , version 1 (09-11-2021)

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Angus J Dunnett, Duncan Gowland, Christine M Isborn, Alex W. Chin, Tim J Zuehlsdorff. Influence of non-adiabatic effects on linear absorption spectra in the condensed phase: Methylene blue. The Journal of Chemical Physics, 2021, ⟨10.1063/5.0062950⟩. ⟨hal-03423096⟩
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