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Herzberg–Teller coupling in coherent multidimensional spectroscopy: Analytical response functions for multilevel systems.

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Bibliographic Details
Title: Herzberg–Teller coupling in coherent multidimensional spectroscopy: Analytical response functions for multilevel systems.
Authors: Troiani, Filippo
Source: Journal of Chemical Physics; 3/28/2026, Vol. 164 Issue 12, p1-20, 20p
Subject Terms: ELECTRONIC systems, COUPLING agents (Chemistry), FOURIER analysis, PYTHON programming language
Company/Entity: GITHUB Inc.
Abstract: Coherent multidimensional spectroscopy enables detailed investigations of vibronic effects in molecular and solid-state systems. We present explicit analytical expressions for multidimensional nonlinear response functions in the presence of Herzberg–Teller (non-Condon) coupling, within the displaced harmonic oscillator model. The formulation applies to electronic systems with an arbitrary number N of electronic states and to response functions of arbitrary order M in the light–matter interaction. We show that Herzberg–Teller coupling introduces additional oscillatory factors in the time-domain response functions, leading, upon Fourier transformation, to replicas of the Franck–Condon multidimensional spectra shifted by integer multiples of the vibrational frequencies. The present results provide a general analytical framework for the interpretation of non-Condon effects in coherent multidimensional spectroscopies. A Python code that implements the present approach and simulates multidimensional spectra for N-level systems is available on GitHub. [ABSTRACT FROM AUTHOR]
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Database: Complementary Index
Description
Abstract:Coherent multidimensional spectroscopy enables detailed investigations of vibronic effects in molecular and solid-state systems. We present explicit analytical expressions for multidimensional nonlinear response functions in the presence of Herzberg–Teller (non-Condon) coupling, within the displaced harmonic oscillator model. The formulation applies to electronic systems with an arbitrary number N of electronic states and to response functions of arbitrary order M in the light–matter interaction. We show that Herzberg–Teller coupling introduces additional oscillatory factors in the time-domain response functions, leading, upon Fourier transformation, to replicas of the Franck–Condon multidimensional spectra shifted by integer multiples of the vibrational frequencies. The present results provide a general analytical framework for the interpretation of non-Condon effects in coherent multidimensional spectroscopies. A Python code that implements the present approach and simulates multidimensional spectra for N-level systems is available on GitHub. [ABSTRACT FROM AUTHOR]
ISSN:00219606
DOI:10.1063/5.0322870