Theory of two-dimensional spectroscopy with intense laser fields

Bressan, Giovanni ORCID: and van Thor, Jasper J. (2021) Theory of two-dimensional spectroscopy with intense laser fields. The Journal of Chemical Physics, 154 (24). ISSN 0021-9606

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Two-dimensional vibrational and electronic spectroscopic observables of isotropically oriented molecular samples in solution are sensitive to laser field intensities and polarization. The third-order response function formalism predicts a signal that grows linearly with the field strength of each laser pulse, thus lacking a way of accounting for non-trivial intensity-dependent effects, such as saturation and finite bleaching. An analytical expression to describe the orientational part of the molecular response, which, in the weak-field limit, becomes equivalent to a four-point correlation function, is presented. Such an expression is evaluated for Liouville-space pathways accounting for diagonal and cross peaks for all-parallel and cross-polarized pulse sequences, in both the weak- and strong-field conditions, via truncation of a Taylor series expansion at different orders. The results obtained in the strong-field conditions suggest how a careful analysis of two-dimensional spectroscopic experimental data should include laser pulse intensity considerations when determining molecular internal coordinates.

Item Type: Article
Additional Information: Funding information: G.B. and J.J.v.T. acknowledge support from The Leverhulme Trust under Award No. RPG-2018-372.
Uncontrolled Keywords: physics and astronomy(all),physical and theoretical chemistry ,/dk/atira/pure/subjectarea/asjc/3100
Faculty \ School: Faculty of Science > School of Chemistry
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Depositing User: LivePure Connector
Date Deposited: 14 Jul 2021 00:29
Last Modified: 23 Oct 2022 02:39
DOI: 10.1063/5.0051435


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