Water pair potential of near spectroscopic accuracy. II. Vibration-rotation-tunneling levels of the water dimer
Water pair potential of near spectroscopic accuracy. II. Vibration-rotation-tunneling levels of the water dimer
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DOI：
10.1063/1.1311290
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发表时间：
2000-10-22
影响因子：
4.4
通讯作者：
Szalewicz, K
中科院分区：
文献类型：
--
作者：
Groenenboom, GC;Wormer, PES;Szalewicz, K
对于旋转量子数 J 和 K 小于或等于 2 的值，对水二聚体的振动-旋转-隧道 (VRT) 能级进行近乎精确的六维量子计算表明，上一篇论文（论文 I）中提出的 SAPT-5s 水对势很好地表示了水二聚体的实验高分辨率远红外光谱。在分析了跃迁频率相对于电势线性参数的敏感性之后，我们可以通过仅使用 (H2O)(2) 中通过实验确定的基态隧道分裂之一来进一步提高该电势。所得水对电势 SAPT-5st 的准确性是通过与 (H2O)(2) 和 (D2O)(2) 的光谱数据进行比较而确定的：基态和激发态隧道分裂和旋转常数，以及分子间振动的频率。 (C) 2000 年美国物理研究所。 [S0021-9606(00)30240-9]。
Nearly exact six-dimensional quantum calculations of the vibration-rotation-tunneling (VRT) levels of the water dimer for values of the rotational quantum numbers J and K less than or equal to2 show that the SAPT-5s water pair potential presented in the preceding paper (paper I) gives a good representation of the experimental high-resolution far-infrared spectrum of the water dimer. After analyzing the sensitivity of the transition frequencies with respect to the linear parameters in the potential we could further improve this potential by using only one of the experimentally determined tunneling splittings of the ground state in (H2O)(2). The accuracy of the resulting water pair potential, SAPT-5st, is established by comparison with the spectroscopic data of both (H2O)(2) and (D2O)(2): ground and excited state tunneling splittings and rotational constants, as well as the frequencies of the intermolecular vibrations. (C) 2000 American Institute of Physics. [S0021-9606(00)30240-9].