Karplus-type relationships between scalar coupling constants:: 3JHH molecular versus 4hJHH supramolecular coupling constants

被引：10

作者：

Alkorta, I ^{[1
]}

Elguero, J ^{[1
]}

机构：

[1] CSIC, Inst Quim Med, E-28006 Madrid, Spain

来源：

THEORETICAL CHEMISTRY ACCOUNTS | 2004年 / 111卷 / 01期

关键词：

coupling constants; Karplus relationship; hydrogen bonds; density functional theory calculations;

D O I：

10.1007/s00214-003-0486-7

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 (3)J(HH) coupling constants in six H-X-Y-H systems (ethane, methylamine, methanol, hydrazine, hydroxylamine and hydrogen peroxide) and (4h)J(HH) coupling constants in four H-X...H...Y-H, namely [H3N...H...NH3](+) (two arrangements), HOH...NH3 and HOH...OH2 have been calculated theoretically as a function of the torsion angle phi. For covalent situations, the corresponding Karplus equations have been fitted to calculated (3)J(HH)=acos2phi+bcosphi+c. The a, b and c terms have been analyzed as a function of the electronegativities of X and Y. In the case of ammonium/ammonia complexes (proton shared and not), water/ammonia, and water dimer the values are low (maximum 0.5 Hz) but follow closely a Karplus relationship. Supplementary material is available in the online version of this article at http://dx.dol.org/10.1007/s00214-003-0486-7.

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页码：31 / 35

页数：5

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