OH ^-阴离子的近光谱性质的完全{\it ab initio}势曲线：关联四重激发和标量相对论效应的重要性
A fully {\it ab initio} potential curve of near-spectroscopic quality for the OH^- anion: importance of connected quadruple excitations and scalar relativistic effects
摘要：
对羟基阴离子OH ^{-}的基态电势曲线进行了基准研究，包括1粒子和n粒子基组的详细校准。CCSD（T）基组极限高估了$ω_e$约10 cm ^{-1}，这只能通过在耦合团簇展开中包含连接的四重激发--或者等效地，在多参考计算的有效空间中包含$2π$轨道来补救。在包含标量相对论效应（$ω_e$上的~3 cm ^{-1}）后，获得光谱质量（亚cm ^{-1}精度）的势曲线。我们最好的计算EA（OH），1.828 eV，同意小数点后三位的最佳实验值。我们计算的最佳离解能D_0（OH ^-）= 4.7796 eV和D_0（OH）= 4.4124 eV表明实验D_0（OH）= 4.392 eV可能偏低了0.02 eV。
英文摘要：
A benchmark study has been carried out on the ground-state potential curve of the hydroxyl anion, OH^{-}, including detailed calibration of both the 1-particle and n-particle basis sets. The CCSD(T) basis set limit overestimates $ω_e$ by about 10 cm^{-1}, which is only remedied by inclusion of connected quadruple excitations in the coupled cluster expansion --- or, equivalently, the inclusion of the $2π$ orbitals in the active space of a multireference calculation. Upon inclusion of scalar relativistic effects (-3 cm^{-1} on $ω_e$), a potential curve of spectroscopic quality (sub-cm^{-1} accuracy) is obtained. Our best computed EA(OH), 1.828 eV, agrees to three decimal places with the best available experimental value. Our best computed dissociation energies, D_0(OH^-)=4.7796 eV and D_0(OH)=4.4124 eV, suggest that the experimental D_0(OH)=4.392 eV may possibly be about 0.02 eV too low.
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