Efficient Simulation of Higher-Order Transitions in Resonance Raman Spectroscopy and Its Chiral Extension.
- 1Scuola Normale Superiore , Piazza dei Cavalieri 7, 56126Pisa, Italy.
Abstract
We present an automated path-integral generator for resonance Raman (RR) calculations supporting Herzberg-Teller effects and Duschinsky rotation, and able to treat any type of vibrational transition, including overtones, combination bands, as well as hot bands. The method constructs the required tensor invariants directly from low-rank intermediates, avoiding both transition-specific manual derivations and the explicit construction of high-order correlation functions. The generated expressions are canonicalized symbolically and evaluated through optimized contraction paths. Compared to formulations based on explicit high-rank correlation tensors, this substantially lowers the asymptotic cost for several higher-order transition classes while providing a unified workflow for automatic expression generation. We validate the approach for multiple transition families, examine the influence of finite-temperature effects through hot-band contributions, and show how it can be straightforwardly extended to resonance Raman optical activity (RROA).
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BibTeX
@article{bianchi2026efficient,
title = {{Efficient Simulation of Higher-Order Transitions in Resonance Raman Spectroscopy and Its Chiral Extension.}},
author = {Andrea Bianchi and Julien Bloino},
journal = {Journal of chemical theory and computation},
year = {2026},
month = sep,
doi = {10.1021/acs.jctc.6c01051},
url = {https://europepmc.org/article/MED/42917448},
note = {CC BY},
}
RIS
TY - JOUR
TI - Efficient Simulation of Higher-Order Transitions in Resonance Raman Spectroscopy and Its Chiral Extension.
AU - Andrea Bianchi
AU - Julien Bloino
PY - 2026
DA - 2026/09/01
JO - Journal of chemical theory and computation
DO - 10.1021/acs.jctc.6c01051
UR - https://europepmc.org/article/MED/42917448
AB - We present an automated path-integral generator for resonance Raman (RR) calculations supporting Herzberg-Teller effects and Duschinsky rotation, and able to treat any type of vibrational transition, including overtones, combination bands, as well as hot bands. The method constructs the required tensor invariants directly from low-rank intermediates, avoiding both transition-specific manual derivations and the explicit construction of high-order correlation functions. The generated expressions are canonicalized symbolically and evaluated through optimized contraction paths. Compared to formulations based on explicit high-rank correlation tensors, this substantially lowers the asymptotic cost for several higher-order transition classes while providing a unified workflow for automatic expression generation. We validate the approach for multiple transition families, examine the influence of finite-temperature effects through hot-band contributions, and show how it can be straightforwardly extended to resonance Raman optical activity (RROA).
SN - 1549-9618
SN - 1549-9626
ER -