ANGULAR-DEPENDENCE OF GEMINAL SPIN-SPIN COUPLING-CONSTANTS IN A PROTOTYPE CH2 GROUP - J(H,H) VERSUS INTERBOND ANGLE IN METHANE

被引:18
作者
GEERTSEN, J
ODDERSHEDE, J
RAYNES, WT
机构
[1] ODENSE UNIV,DEPT CHEM,DK-5230 ODENSE,DENMARK
[2] UNIV SHEFFIELD,DEPT CHEM,SHEFFIELD S3 7HF,S YORKSHIRE,ENGLAND
关键词
SPIN-SPIN COUPLING; ANGLE VARIATIONS; METHANE;
D O I
10.1002/mrc.1260310806
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Correlated ab initio calculations of the dependences of the proton-proton spin-spin coupling constant J(H-1, H-2) in methane with the variation of the H-1-C-H-2 interbond angle are reported. The other coupling constants, including J(C, H), were simultaneously calculated. The coupling constants J(H-1, H-2) and J(C, H-1) increase nearly linearly with the opening of the interbond angle whereas J(H-2, H-3) and J(C, H-3) decrease. J(H-3, H-4) is only very slightly affected. The changes are due almost solely to changes in the Fermi contact term. The angular dependence is slightly larger at the SCF level of calculation than at the correlated level. The change in the geminal coupling constant J(H-1, H-2) with respect to equilibrium geometry is given to within 0.025 Hz by DELTAJ(H-1, H-2) (Hz) = 41.57 sin alpha12 - 8.90 sin2 alpha12, where alpha12 is the increase in the interbond angle with respect to equilibrium (-10-degrees less-than-or-equal-to alpha12 less-than-or-equal-to 10-degrees).
引用
收藏
页码:722 / 725
页数:4
相关论文
共 22 条
[1]   INTERNAL H-C-C ANGLE DEPENDENCE OF VICINAL H-1-H-1 COUPLING-CONSTANTS [J].
BARFIELD, M ;
SMITH, WB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (05) :1574-1581
[2]   DEPENDENCE OF GEMINAL H-H SPIN-SPIN COUPLING-CONSTANTS ON PHI AND PSI ANGLES OF PEPTIDES IN SOLUTION [J].
BARFIELD, M ;
HRUBY, VJ ;
MERALDI, JP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (06) :1308-1314
[3]   CONFORMATIONAL EQUILIBRIA IN NITROGEN-CONTAINING SATURATED 6-MEMBERED RINGS [J].
CRABB, TA .
ADVANCES IN HETEROCYCLIC CHEMISTRY, 1984, 36 :1-173
[4]   NUCLEAR-SPIN SPIN COUPLING IN THE METHANE ISOTOPOMERS [J].
GEERTSEN, J ;
ODDERSHEDE, J ;
RAYNES, WT ;
SCUSERIA, GE .
JOURNAL OF MAGNETIC RESONANCE, 1991, 93 (03) :458-471
[5]  
GERTSEN J, IN PRESS
[6]   ANHARMONIC-FORCE FIELD AND EQUILIBRIUM STRUCTURE OF METHANE [J].
GRAY, DL ;
ROBIETTE, AG .
MOLECULAR PHYSICS, 1979, 37 (06) :1901-1920
[7]   ANGULAR DEPENDENCE OF ELECTRON-COUPLED PROTON INTERACTIONS IN CH2 GROUPS [J].
GUTOWSKY, HS ;
KARPLUS, M ;
GRANT, DM .
JOURNAL OF CHEMICAL PHYSICS, 1959, 31 (05) :1278-1289
[8]  
JAMESON CJ, 1987, MULTINUCLEAR NMR, P108
[9]   CONTACT ELECTRON-SPIN COUPLING OF NUCLEAR MAGNETIC MOMENTS [J].
KARPLUS, M .
JOURNAL OF CHEMICAL PHYSICS, 1959, 30 (01) :11-15
[10]  
Klessinger M., 1988, J MOL STRUC-THEOCHEM, V169, P119