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Volume 221, 2020

Modeling multidimensional spectral lineshapes from first principles: application to water-solvated adenine

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Abstract

In this discussion we present a methodology to describe spectral lineshape from first principles, providing insight into the solvent–solute molecular interactions in terms of static and dynamic disorder and how these shape the signals recorded experimentally in linear and nonlinear optical spectroscopies, including two-dimensional electronic spectroscopy (2DES). Two different strategies for simulating the lineshape are compared: both rely on the same evaluation of the coupling between the electronic states and the intra-molecular vibrations, while they differ in describing the influence exerted by the diverse water configurations attained along a molecular dynamics (MD) simulation. The first method accounts for such water arrangements as first order perturbations on the adenine energies computed for a single reference (gas phase) quantum calculation. The second method requires computation of the manifold of excited states explicitly at each simulation snapshot, employing a hybrid quantum mechanics/molecular mechanics (QM/MM) scheme. Both approaches are applied to a large number of states of the adenine singlet excited manifold (chosen because of its biological role), and compared with available experimental data. They give comparable results but the first approach is two orders of magnitude faster. We show how the various contributions (static/dynamic disorder, intra-/inter-molecular interactions) sum up to build the total broadening observed in experiments.

Graphical abstract: Modeling multidimensional spectral lineshapes from first principles: application to water-solvated adenine

Associated articles

Article information


Submitted
22 May 2019
Accepted
20 Jun 2019
First published
20 Jun 2019

Faraday Discuss., 2020,221, 219-244
Article type
Paper

Modeling multidimensional spectral lineshapes from first principles: application to water-solvated adenine

J. Segarra-Martí, F. Segatta, T. A. Mackenzie, A. Nenov, I. Rivalta, M. J. Bearpark and M. Garavelli, Faraday Discuss., 2020, 221, 219 DOI: 10.1039/C9FD00072K

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