基于高斯玻色采样的内转换路径分辨分析

中文摘要 AI 辅助

高斯玻色采样（GBS）已为量子优势提供了有力证据，激发了寻找实际应用的探索。此类应用依赖于将物理问题映射到GBS的原生输出：从高度非平凡的几率分布中采样的光子数模式。在此，我们推导出内转换（IC）速率常数 $k_\mathrm{IC}$ 的GBS兼容映射，并纳入两个重要的物理效应——Duschinsky旋转和Herzberg-Teller贡献。我们利用二苯并三联苯的采样模拟验证了这一框架，重现了 $k_\mathrm{IC}$ 的报道值。除了 $k_\mathrm{IC}$ 的重建，我们还表明GBS的光子数模式编码了负责IC过程的振动模式组合，我们称之为非辐射路径。这些路径分辨数据随后可以以不同方式分组，以提取多个具有物理意义的可观测量。特别是，它支持从单个模式和模式族贡献到多个路径共享的重复振动构型等多个层级的 $k_\mathrm{IC}$ 分析。我们发现Duschinsky旋转将相关振动路径相关的 $k_\mathrm{IC}$ 比例从46%增加到86%，并识别出具有最大速率贡献的模式组合。这些路径分辨的见解可以指导有针对性的分子修饰，包括选择性氘化和键取代，以控制非辐射衰变。

英文摘要

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 $k_\mathrm{IC}$ 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 $k_\mathrm{IC}$. Beyond $k_\mathrm{IC}$ 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 $k_\mathrm{IC}$ 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 $k_\mathrm{IC}$ 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.

发表机构

• Paderborn University（帕德博恩大学）
• University of Helsinki（赫尔辛基大学）

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