H2O2分子高激发振转能级的变分计算
Variational calculation of highly excited rovibrational energy levels of H2O2
摘要：
本文给出了H_2 O_2电子基态转动-振动能级的高精度从头变分计算结果。这些结果使用最近计算的势能面和变化的核运动程序WARV 4，它使用一个精确的动能（EKE）运营商，和TROVE，它使用的动能的数值扩展。TROVE计算是针对旋转激励高值（$J$高达35）的水平进行的。转振能级的纯\ai \计算再现了具有约1 \cm的标准偏差的观察到的能级，类似于$J = 0$计算的标准偏差，因为在给定振动状态内的旋转能量的理论和实验之间的差异基本上由振动带原点中的误差确定。对从头算平衡几何形状和扭转势垒的高度进行了微小的调整。使用这些并使用$J = 0$状态中的误差校正能带起源将观测到的$-$计算能量的标准偏差降低到仅0.002 \cm \（对于高达$J = 10$的能级）和0.02 \cm \（对于所有实验已知的能级，其延伸至$J = 35$）。
英文摘要：
Results are presented for highly accurate ab initio variational calculation of the rotation - vibration energy levels of H2O2 in its electronic ground state. These results use a recently computed potential energy surface and the variational nuclear-motion programmes WARV4, which uses an exact kinetic energy (EKE) operator, and TROVE, which uses a numerical expansion for the kinetic energy. The TROVE calculations are performed for levels with high values of rotational excitation, $J$ up to 35. The purely \ai\ calculations of the rovibrational energy levels reproduce the observed levels with a standard deviation of about 1 \cm, similar to that of the $J = 0$ calculation as the discrepancy between theory and experiment for rotational energies within a given vibrational state is substantially determined by the error in the vibrational band origin. Minor adjustments are made to the ab initio equilibrium geometry and to the height of the torsional barrier. Using these and correcting the band origins using the error in $J = 0$ states lowers the standard deviation of the observed $-$ calculated energies to only 0.002 \cm\ for levels up to $J = 10$ and 0.02 \cm\ for all experimentally know energy levels, which extend up to $J = 35$.
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