Pathway-resolved analysis of internal conversion enabled by Gaussian boson sampling

Abstract

Gaussian Boson Sampling (GBS) has provided strong evidence of quantum advantage, motivating the search for real-world applications. Such applications rely on mapping physical problems to the native GBS output: photon-number patterns sampled from a highly non-trivial probability distribution. Here we derive a GBS-compatible mapping for the rate constant kIC of internal conversion (IC), incorporating two important physical effects -- Duschinsky rotations and Herzberg--Teller contribution. We validate this framework using sampling \textit{simulations} of dibenzoterrylene, reproducing reported values of kIC. Beyond kIC reconstruction, we show that the photon-number patterns of GBS encode the vibrational mode combinations responsible for the IC process, which we refer to as non-radiative pathways. This pathway-resolved data can then be grouped in different ways to extract multiple physically motivated observables. In particular, it enables kIC analysis at several levels, from individual modes and mode family contributions to recurring vibrational configurations shared by multiple pathways. We find that Duschinsky rotations increase the fraction of kIC associated with correlated vibrational pathways from 46% to 86%, and identify the mode combinations with the largest rate contributions. These pathway-resolved insights can guide targeted molecular modifications, including selective deuteration and bond substitution, to control non-radiative decay.

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BibTeX RIS

BibTeX

@misc{roiz2026pathwayresolved,
  title = {{Pathway-resolved analysis of internal conversion enabled by Gaussian boson sampling}},
  author = {Mikhail Roiz and Rashid Valiev and Jan-Lucas Eickmann and Theo Kurten and Benjamin Brecht and Michael Stefszky and Christine Silberhorn},
  howpublished = {arXiv},
  year = {2026},
  month = oct,
  doi = {10.48550/arxiv.2610.03271},
  eprint = {2610.03271},
  archivePrefix = {arXiv},
  url = {https://arxiv.org/abs/2610.03271},
  note = {CC BY 4.0},
}

RIS

TY  - UNPB
TI  - Pathway-resolved analysis of internal conversion enabled by Gaussian boson sampling
AU  - Mikhail Roiz
AU  - Rashid Valiev
AU  - Jan-Lucas Eickmann
AU  - Theo Kurten
AU  - Benjamin Brecht
AU  - Michael Stefszky
AU  - Christine Silberhorn
PY  - 2026
DA  - 2026/10/02
PB  - arXiv
DO  - 10.48550/arxiv.2610.03271
UR  - https://arxiv.org/abs/2610.03271
AB  - Gaussian Boson Sampling (GBS) has provided strong evidence of quantum advantage, motivating the search for real-world applications. Such applications rely on mapping physical problems to the native GBS output: photon-number patterns sampled from a highly non-trivial probability distribution. Here we derive a GBS-compatible mapping for the rate constant k_IC of internal conversion (IC), incorporating two important physical effects -- Duschinsky rotations and Herzberg--Teller contribution. We validate this framework using sampling \textit{simulations} of dibenzoterrylene, reproducing reported values of k_IC. Beyond k_IC reconstruction, we show that the photon-number patterns of GBS encode the vibrational mode combinations responsible for the IC process, which we refer to as non-radiative pathways. This pathway-resolved data can then be grouped in different ways to extract multiple physically motivated observables. In particular, it enables k_IC analysis at several levels, from individual modes and mode family contributions to recurring vibrational configurations shared by multiple pathways. We find that Duschinsky rotations increase the fraction of k_IC associated with correlated vibrational pathways from 46% to 86%, and identify the mode combinations with the largest rate contributions. These pathway-resolved insights can guide targeted molecular modifications, including selective deuteration and bond substitution, to control non-radiative decay.
ER  -

Abstract

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