Herzberg-Teller coupling in coherent multidimensional spectroscopy: analytical response functions for multilevel systems
Fuente:
arXiv
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| Formato: | Preprint |
| Publicado: |
2026
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| _version_ | 1866912981147713536 |
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| author | Troiani, Filippo |
| author_facet | Troiani, Filippo |
| contents | 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. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2601_09346 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Herzberg-Teller coupling in coherent multidimensional spectroscopy: analytical response functions for multilevel systems Troiani, Filippo Quantum Physics 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. |
| title | Herzberg-Teller coupling in coherent multidimensional spectroscopy: analytical response functions for multilevel systems |
| topic | Quantum Physics |
| url | https://arxiv.org/abs/2601.09346 |