Various types of hydrogen bonds have been recognized during the past century. In this research, a new type of noncovalent interaction, the dipole-induced hydrogen bond formed between a hydrogen molecule and an alkali halide, H–H···F–M, is studied. Proposed by Zhang and co-workers (Phys. Chem. Chem. Phys.2015, 17, 20361), these systems are extensively investigated initially using the “gold standard” CCSD(T) method in conjunction with augmented correlation-consistent polarized core–valence basis sets up to quadruple-ζ. The full triple excitations CCSDT method has been used to further refine the energies. Several properties including geometries, bond energies, vibrarional frequencies, charge distributions, and dipole moments have been reported. The earlier Zhang research considered only the linear H–H···F–M structures. However, we find these linear stationary points to be separated by very small barriers from the much lower lying bent C_s structures. The CCSDT/aug-cc-pCVQZ(-PP) method predicts the dissociation energies for bent H–H···F–M (M = Li, Na, K, Rb, Cs) are 2.76, 2.96, 3.00, 2.89, and 2.49 kcal mol^–1, respectively, suggesting that the H···F hydrogen bond becomes gradually stronger when alkali metal M goes down the periodic table from Li to K but becomes slightly weaker for Rb and even more for Cs. This Li < Na < K > Rb > Cs order is consistent with that for the dipole moments for the isolated MF (M = Li, Na, K, Rb, Cs) diatomics. Symmetry adapted perturbation theory (SAPT) is used to understand these unusual noncovalent interactions.

中文翻译：

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分子氢与碱金属氟化物之间的非共价相互作用：H–H··F–M（M = Li，Na，K，Rb，Cs）。高级理论预测和SAPT分析

在过去的一个世纪中，人们已经认识到各种类型的氢键。在这项研究中，研究了一种新型的非共价相互作用，即氢分子与碱金属卤化物H–H··F–M之间形成的偶极诱导的氢键。张建议和同事（物理学，化学，化学物理，2015年，17，20361），最初使用“黄金标准” CCSD（T）方法以及增强的相关性一致的极化核-价基数集达到四倍ζ，对这些系统进行了广泛的研究。全三次激发CCSDT方法已被用来进一步完善能量。已经报道了几种性质，包括几何形状，键能，振动频率，电荷分布和偶极矩。Zhang的早期研究仅考虑线性H–H··F–M结构。但是，我们发现这些线性固定点与非常低的弯曲C _s结构之间的障碍很小。CCSDT / aug-cc-pCVQZ（-PP）方法预测弯曲H–H··F–M（M = Li，Na，K，Rb，Cs）的解离能为2.76、2.96、3.00、2.89，和2.49 kcal mol分别为^–1，表明当碱金属M从Li到K下降到元素周期表时，H···F氢键逐渐变强，但Rb变得更弱，Cs变得更弱。Li <Na <K> Rb> Cs的阶与孤立的MF（M = Li，Na，K，Rb，Cs）双原子的偶极矩的阶一致。对称适应扰动理论（SAPT）用于理解这些异常的非共价相互作用。