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首页> 外文期刊>The Journal of Chemical Physics >HF dimer: Empirically refined analytical potential energy and dipole hypersurfaces from ab initio calculations [Review]
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HF dimer: Empirically refined analytical potential energy and dipole hypersurfaces from ab initio calculations [Review]

机译：HF二聚体：从头算计算中根据经验精炼的分析势能和偶极超表面[综述]

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摘要

The interaction between two HF molecules as a function of all six internal coordinates is reported as calculated for 3284 selected points in configuration space at counterpoise-corrected explicitly correlated levels and fitted to an analytical expression, which is described in detail. The unweighted rms deviation for all 3284 points is 21 cm(-1). Empirical refinements are applied through mixing and scaling of the ab initio data, guided by the comparison of multidimensional nuclear quantum energy levels with experimental data. The resulting semiempirical pair potentials (labeled SC-2.9 and SO-3) contain 67 and 61 freely adjusted parameters and are combined with a four parameter monomer potential of generalized Poschl-Teller type. Various minimum energy paths and cuts are investigated. Major improvements over earlier HF dimer potentials are demonstrated via multidimensional solutions of the nuclear Schrodinger equation. Comparison with other high level ab initio calculations and with various experimental data reveals very good overall consistency. The new potential suggests strong Coriolis coupling in the librational degrees of freedom. Best estimates of stationary points, of the dimer dissociation energy (D-e=19.1+/-0.2 kJ/mol), of the electronic barrier to hydrogen bond exchange (4.2+/-0.2 kJ/mol), of the electronic barrier to linearity (3.9+/-0.2 kJ/mol), and of the electronic barrier to hydrogen exchange (175+/-10 kJ/mol) are inferred. Based on accurate electric dipole functions for the monomer and distortion contributions calculated with a large basis at SCF level, a simple analytical six-dimensional electric dipole hypersurface is presented. (C) 1998 American Institute of Physics. [References: 107]
机译：据报道，两个HF分子之间的相互作用是所有六个内部坐标的函数，是针对配置空间中3284个选定点的计算，这些点在平衡地校正的显式相关水平处进行拟合，并适合于分析表达式，对此进行了详细描述。所有3284点的未加权均方根偏差为21 cm（-1）。通过对从头算数据进行混合和缩放来进行经验改进，以多维核量子能级与实验数据的比较为指导。所得的半经验对电势（标记为SC-2.9和SO-3）包含67和61个自由调节的参数，并与广义Poschl-Teller型的四参数单体电势组合。研究了各种最小的能量路径和削减。通过核薛定inger方程的多维解证明了对较早的HF二聚体电势的重大改进。与其他高级从头算计算以及各种实验数据进行比较，您可以得出非常好的整体一致性。新的潜力表明在自由度上有很强的科里奥利耦合。对氢键交换的电子势垒（4.2 +/- 0.2 kJ / mol），对线性的电子势垒（二聚物解离能（De = 19.1 +/- 0.2 kJ / mol），电子势垒的固定点的最佳估计）推断出3.9 +/- 0.2kJ / mol）和氢交换的电子势垒（175 +/- 10kJ / mol）。基于对单体的精确电偶极函数和在SCF级别上大量计算出的畸变贡献，提出了一种简单的解析六维电偶极超表面。 （C）1998美国物理研究所。 [参考：107]

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