Characteristics of hydrogen bond revealed from water clusters
Characteristics of hydrogen bond revealed from water clusters
复制标题
水团簇揭示的氢键特征
DOI：
10.1140/epjd/e2014-50027-5
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发表时间：
2014-09
影响因子：
1.8
通讯作者：
Yuehong Yin
中科院分区：
文献类型：
--
作者：
Hongshan Chen;Cairong Zhang;Yan Zhang;Yuehong Yin
氢键网络是水的特殊物理化学性质的重要组成部分，然而，氢键的描述仍然是凝聚水研究的一个挑战。水分子团簇的结构和键合性质的研究为理解水分子中氢键提供了一把钥匙。本文定义了一组新的几何参数来描述给体OH的成键轨道与受体分子孤对电子的非成键轨道之间的重叠程度。这种轨道重叠对氢键的强度起着主导作用。研究了水二聚体的结合能与这些参数的关系。结果表明，这些参数能较好地描述氢键强度。水六聚体的环、书、笼和棱柱异构体形成6、7、8和9氢键，并且这些异构体中的键合强度显著变化。（H2O）n = 17，19和21的内溶剂化和全表面结构几乎是等能的。内部溶剂化的异构体形成较少但较强的H-键。对上述团簇中的氢键进行了详细的研究。几何参数能很好地描述氢键的性质，并与氢键强度有很好的相关性。对于形成较强氢键的结构，氢键长度较短，角度参数更接近最佳值，其均方根偏差较小。DDAA和DDA分子作为H-供体产生的H-键相对较弱。研究了（H2O）n（n= 17，19和21）的振动光谱。分子内OH键的伸缩振动对其成键环境敏感。由几何参数判断的氢键强度与由拉伸频率判断的氢键强度吻合较好。
The hydrogen bond network is responsible for the exceptional physical and chemical properties of water, however, the description of hydrogen bond remains a challenge for the studies of condensed water. The investigation of structural and binding properties of water clusters provides a key for understanding the H-bonds in bulk water. In this paper, a new set of geometric parameters are defined to describe the extent of the overlap between the bonding orbital of the donor OH and the nonbonding orbital of the lone-pair of the acceptor molecule. This orbital overlap plays a dominant role for the strength of H-bonds. The dependences of the binding energy of the water dimer on these parameters are studied. The results show that these parameters properly describe the H-bond strength. The ring, book, cage and prism isomers of water hexamer form 6, 7, 8 and 9 H-bonds, and the strength of the bonding in these isomers changes markedly. The internally-solvated and the all-surface structures of (H2O)nforn= 17, 19 and 21 are nearly isoenergetic. The internally-solvated isomers form fewer but stronger H-bonds. The hydrogen bonding in the above clusters are investigated in detail. The geometric parameters can well describe the characters of the H-bonds, and they correlate well with the H-bond strength. For the structures forming stronger H-bonds, the H-bond lengths are shorter, the angle parameters are closer to the optimum values, and their rms deviations are smaller. The H-bonds emanating from DDAA and DDA molecules as H-donor are relatively weak. The vibrational spectra of (H2O)n(n= 17, 19 and 21) are studied as well. The stretching vibration of the intramolecular OH bond is sensitive to its bonding environment. The H-bond strength judged from the geometric parameters is in good agreement with the bonding strength judged from the stretching frequencies.
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影响因子：
64.8
作者：
C. Bawn
通讯作者：
C. Bawn
DOI：
10.1021/j100122a005
发表时间：
1993-05
期刊：
The Journal of Physical Chemistry
影响因子：
--
作者：
C. J. Tsai;K. Jordan
通讯作者：
C. J. Tsai;K. Jordan
影响因子：
2.9
作者：
Cruzan, JD;Viant, MR;Saykally, RJ
通讯作者：
Saykally, RJ
影响因子：
2.9
作者：
Shields, Robert M.;Temelso, Berhane;Shields, George C.
通讯作者：
Shields, George C.
影响因子：
3.3
作者：
B. Hartke
通讯作者：
B. Hartke