AI 中文总结
本文将Wilson-Hamiltonian框架扩展为适用于强磁场下双原子分子振转光谱计算的三维量子力学框架，揭示了磁场对光谱及分子结构的影响，成果可用于高场光谱与天体化学建模。
AI 中文摘要
由于缺乏强磁场下分子光谱的实验数据，高分辨率且可靠的计算光谱对于解读从强磁性天体收集的光谱至关重要。本文将Wilson-Hamiltonian框架（该框架已由我们实现并在《J. Chem. Theory Comput.》21卷9753页（2025年）进行了基准测试）扩展为通用三维框架，适用于计算强均匀磁场下双原子分子的振转光谱。与磁场相关的电子和原子核哈密顿量完整捕获了粒子运动与磁场之间的非微扰耦合，使该方法适用于所有场强。本文还对外部静磁场下振转跃迁的电四极跃迁矩积分进行了公式化、实现和计算，得到的光谱符合分子-磁场系统的选择定则。研究记录了随场强增加出现的光谱变化，如峰的位移、分裂、合并、出现和消失；还分别研究了电子和原子核的贡献，以及两者的共同贡献，揭示了诸如键的硬化、旋转势垒的出现、场诱导的态耦合/去耦合，以及旋转和振动态的对称性破缺等潜在物理机制。这些结果提供了^1H₂在极端磁场环境下振转特征的首个全量子力学计算结果，其精度适用于实验解读。本文开发的方法与高场光谱和天体化学建模直接相关，既可以提供计算数据，也有助于理解强磁场对分子电子结构和核运动的光谱影响。
英文摘要
In the absence of experimental data for molecular spectra in strong magnetic fields, high resolution and reliable computational spectra are required for the interpretation of spectra collected from highly magnetic astrophysical objects. In this paper, we extend the Wilson-Hamiltonian framework, recently implemented and benchmarked by us (\textit{J. Chem. Theory Comput.}, \textbf{21}, 9753 (2025) ), to a general three-dimensional framework suitable for computing the rovibrational spectra of diatomic molecules in strong uniform magnetic fields. The field-dependent electronic and nuclear Hamiltonians capture full non-perturbative coupling between particle motion and the field making the method applicable to all field strengths. The electric quadrupole transition moment integrals for rovibrational transitions in external static magnetic fields are formulated, implemented, and computed to yield spectra which respect the selection rules of the molecule-field system. The spectral changes with increasing field strength such as shifting, splitting, merging, appearance and disappearance of peaks are noted. Contributions from electrons and nuclei are studied individually, as well as in unison to reveal the underlying physics such as stiffening of the bond, emergence of a rotational barrier, field-induced coupling/decoupling of states, and symmetry-breaking in rotational and vibrational states. These results provide the first fully quantum mechanical computational results for the rovibrational signature of $^1\mathrm{H}_{2}$ in extreme magnetic field environments with accuracy suitable for experimental interpretation. The methodology developed herein has direct relevance for high-field spectroscopy and astrochemical modeling, both for providing computational data as well as for understanding the spectral impact of strong magnetic fields on electronic structure and nuclear motion in molecules.
