Modeling multidimensional spectral lineshapes from first principles: Application to water-solvated adenine
File(s)
Accepted version
Author(s)
Type
Journal Article
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, in which both the coupling to the intra-molecular vibrations and the influence exerted by the different water distributions attained along a molecular dynamics (MD) simulation are accurately described. 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 to compute 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.
Date Issued
2020-01-01
Date Acceptance
2019-06-20
Citation
Faraday Discussions, 2020, 221, pp.219-244
ISSN
1359-6640
Publisher
Royal Society of Chemistry (RSC)
Start Page
219
End Page
244
Journal / Book Title
Faraday Discussions
Volume
221
Copyright Statement
© 2019 Royal Society of Chemistry.
Sponsor
European Commission
Grant Number
Marie Sklodowska Curie Actions (MSCA-IF)
Subjects
Science & Technology
Physical Sciences
Chemistry, Physical
Chemistry
2ND-ORDER PERTURBATION-THEORY
EXCITATION-ENERGY TRANSFER
MOLECULAR WAVE-FUNCTIONS
ANO BASIS-SETS
ELECTRONIC SPECTROSCOPY
FOURIER-TRANSFORM
EXCITED-STATES
DNA
FLUORESCENCE
ABSORPTION
0306 Physical Chemistry (incl. Structural)
0904 Chemical Engineering
0303 Macromolecular and Materials Chemistry
Chemical Physics
Publication Status
Published
Date Publish Online
2019-06-20