NO$_3$自由基的2500个振动电子本征态
2500 vibronic eigenstates of the NO$_3$ radical
AI总结：
本研究利用包含五个电子态的精确全维度非绝热势，结合张量网络态方法，计算了NO$_3$自由基超过2500个振动电子态，揭示了显著的对称性致能级分裂与非绝热效应，并指出了Born-Oppenheimer近似的误差。
摘要：
硝酸自由基NO$_3$在大气化学中起着重要作用，但其耦合和非谐振的振动电子结构的许多方面仍然难以捉摸。在这里，使用包含五个电子态的精确耦合全维度非绝热势，我们重新审视了与电子$\ ilde X ^2A_2'$态相关的振动电子光谱。使用最近开发的张量网络态方法，我们能够计算超过2500个振动电子态，从而与先前的工作相比，将计算的全维度态的数量增加了50倍。虽然我们对于大多数已分配的振动电子能级与实验取得了良好的一致性，但对于其他几个能级，我们观察到显著的分歧。此外，对于反对称弯曲运动，我们发现了由对称性引起的显著大的能级分裂，其大于零阶参考值。我们讨论了不可忽略的非绝热效应，并表明Born-Oppenheimer近似在光谱中导致了显著的误差。
英文摘要：
The nitrate radical NO$_3$ plays an important role in atmospheric chemistry, yet many aspects of its coupled and anharmonic vibronic structure remain elusive. Here, using an accurate, coupled full-dimensional diabatic potential that includes five electronic states, we revisit the vibronic spectrum associated with the electronic $\tilde X ^2A_2'$ state. Using recently developed tensor network state methods, we are able to compute more than 2500 vibronic states, thereby increasing the number of computed full-dimensional states by a factor of 50, compared to previous work. While we obtain good agreement with experiment for most of the assigned vibronic levels, for several others, we observe striking disagreement. Further, for the antisymmetric bending motion we find remarkably large symmetry-induced level splittings that are larger than the zero-order reference. We discuss non-negligible nonadiabatic effects and show that the Born-Oppenheimer approximation leads to significant errors in the spectrum.
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