关联分子电子结构的腔内光子统计

中文摘要 AI 辅助

量子光学通过光子关联表征光，但从头算腔量子电动力学（QED）目前仅计算了原始场矩。本研究采用QED耦合簇（QED-CCSD-22）密度计算腔耦合分子的腔内光子统计，并通过Pauli-Fierz哈密顿量的精确对角化进行验证。坐标原点或偶极约定的变化会使基态发生相干位移，因此即使对于分子离子，腔场的二阶及高阶累积量也有明确定义。QED哈特利-福克（QED Hartree-Fock）的光子子系统完全相干，因此不变统计量可表征电子-光子关联。场涨落为超泊松分布，其二阶相干度由腔频率而非耦合强度决定，当H₂的腔从5 eV失谐至20 eV时，该值从18.5降至4.9。宇称选择定则使三阶累积量的符号可作为分子电荷不对称性沿腔极化方向取向的探针。

英文摘要

Quantum optics characterizes light through photon correlations, but ab initio cavity quantum electrodynamics (QED) has only calculated raw field moments at present. In this study, intracavity photon statistics of cavity-coupled molecules are computed from QED coupled-cluster (QED-CCSD-22) densities and validated against exact diagonalization of the Pauli-Fierz Hamiltonian. A change of coordinate origin or dipole convention displaces the ground state coherently, so second-order and higher cumulants of the cavity field are well defined even for molecular ions. The photon subsystem of QED Hartree-Fock is exactly coherent, so the invariant statistics measure electron-photon correlation. The field fluctuations are super-Poissonian, and their degree of second-order coherence is set by the cavity frequency rather than by the coupling strength, falling from 18.5 to 4.9 for H2 as the cavity is detuned from 5 to 20 eV. A parity selection rule makes the sign of the third cumulant a probe of the orientation of the molecular charge asymmetry along the cavity polarization.

发表机构

• University of Missouri（密苏里大学）

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