Are the solvent effects on H-bonds a cooperativity with van der Waals interactions?

被引:24
作者
Luck, WAP
Klein, D
机构
[1] Phys. Chem. der Universitat Marburg
关键词
hydrogen bonding; solvent effects; cooperativity; van der Waals interactions;
D O I
10.1016/0022-2860(96)09316-7
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The solvent influence on the strength of H-bonds, observed by the shift Delta nu of the OH or NH stretching band, can be described by a solvent parameter LFM(j) for every solvent j: Delta v(B, solvent(j)) = LMF(j) Delta v(B, vapor). This parameter is independent of the H-bond acceptor B and the donor. It is determined for a series of solvents relative to the solvent shift in CCl4. The solvent influences of weak H-bond accepters are included. The solvent mechanism is very similar to H-bond cooperativity of cations or multiple H-bonds and can be described as a polarization effect of the lone pairs of the bonding XH groups by van der Waals interactions which can be studied by this method, The equations given can predict the not negligible solvent influence on H-bonds. The solvent factors are parallel to the Hildebrand parameters of the solvents or the Gutmann numbers and can be understood in terms of the influence of its intermolecular potentials. There are indications on influences of intermolecular zero point energies in the second approximation.
引用
收藏
页码:83 / 94
页数:12
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