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Herzberg-Teller coupling in coherent multidimensional spectroscopy: Analytical response functions for multilevel
1Centro S3, CNR-Istituto di Nanoscienze, I-41125 Modena, Italy.
The Journal of Chemical Physics
|March 25, 2026
Summary
This study introduces analytical expressions for multidimensional spectroscopy, accounting for Herzberg-Teller coupling. This framework helps interpret non-Condon effects in molecular and solid-state systems.
Area of Science:
- Quantum Chemistry
- Spectroscopy
- Computational Physics
Background:
- Coherent multidimensional spectroscopy is vital for studying vibronic effects.
- Non-Condon effects, arising from Herzberg-Teller coupling, complicate spectral interpretation.
- Existing models often simplify or neglect these crucial coupling effects.
Purpose of the Study:
- To develop a general analytical framework for multidimensional nonlinear response functions including Herzberg-Teller coupling.
- To provide a method for interpreting non-Condon effects in coherent multidimensional spectroscopy.
- To enable accurate spectral simulations for systems with multiple electronic states.
Main Methods:
- Derivation of explicit analytical expressions for multidimensional nonlinear response functions.
- Utilizing the displaced harmonic oscillator model.
- Formulation for an arbitrary number of electronic states (N) and arbitrary order of response functions (M).
Main Results:
- Inclusion of Herzberg-Teller coupling introduces additional oscillatory factors in time-domain response functions.
- Fourier transformation reveals replicas of Franck-Condon spectra shifted by vibrational frequencies.
- A general analytical framework for interpreting non-Condon effects is established.
Conclusions:
- The developed framework provides a robust method for analyzing vibronic effects in spectroscopy.
- This work facilitates a deeper understanding of non-Condon phenomena in molecular and solid-state systems.
- A publicly available Python code aids in simulating and interpreting complex spectroscopic data.
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