发表机构
Stockholm University（斯德哥尔摩大学）
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
本文介绍Psi4开源扩展psi4-cbo，在腔玻恩-奥本海默近似下实现光-物质耦合的电子结构计算，并通过精确QEDFCI参考评估近似适用性，应用于丙烯醛振动强耦合共振定位。
AI 中文摘要
我们介绍了psi4-cbo，这是Psi4程序的一个开源扩展，用于在腔玻恩-奥本海默近似（CBOA）框架内进行模拟。通过将腔光子模式与核坐标同等对待，psi4-cbo将光-物质耦合纳入标准电子结构工作流程中。这些工作流程包括自洽场计算、响应理论、解析梯度、联合海森矩阵以及几何优化。该软件包以可复现性为设计目标，并附有其主要工作流程的实用示例文档。为了评估CBOA框架固有的近似性，我们使用精确的QEDFCI参考。将相关能分解为电子-电子和电子-光子通道，使我们能够精确确定CBOA达到定量充分的临界点。此外，我们强调，由于自洽处理会修饰腔模式，满足实验共振条件是依赖于方法的。作为实际应用，我们研究了振动强耦合下的发色团丙烯醛，并详细说明了如何在修饰后的光子模式上而非裸分子带上定位共振。
英文摘要
We present psi4-cbo, an open-source extension of the Psi4 program for simulations within the cavity Born-Oppenheimer Approximation (CBOA). By treating the cavity photon mode on the same footing as the nuclear coordinates, \texttt{psi4-cbo} incorporates light-matter coupling into standard electronic structure workflows. These workflows include self-consistent field calculations, response theory, analytic gradients, joint Hessians, and geometry optimization. The package is designed for reproducibility and is documented with working examples for its main workflows. To evaluate the approximations inherent to the CBOA framework, we use an exact \gls{qedfci} reference. Resolving the correlation energy into electron-electron and electron-photon channels enables us to precisely determine the point at which the CBOA becomes quantitatively sufficient. Additionally, we highlight that, since self-consistent treatments dress the cavity modes, satisfying experimental resonance conditions is method-dependent. As a practical application, we investigate the chromophore acrolein under vibrational strong coupling and detail how to locate resonances on the dressed photon modes rather than the bare molecular bands.
