Karplus equation explained

The Karplus equation, named after Martin Karplus, describes the correlation between ³J-coupling constants and dihedral torsion angles in nuclear magnetic resonance spectroscopy:^[1]

J(\phi) = A \cos ^{2} \phi + B \cos\phi + C

where J is the ³J coupling constant,

\phi is the dihedral angle, and A, B, and C are empirically derived parameters whose values depend on the atoms and substituents involved.^[2] The relationship may be expressed in a variety of equivalent ways e.g. involving cos 2φ rather than cos² φ —these lead to different numerical values of A, B, and C but do not change the nature of the relationship.

The relationship is used for ³J_H,H coupling constants. The superscript "3" indicates that a ¹H atom is coupled to another ¹H atom three bonds away, via H-C-C-H bonds. (Such hydrogens bonded to neighbouring carbon atoms are termed vicinal).^[3] The magnitude of these couplings are generally smallest when the torsion angle is close to 90° and largest at angles of 0 and 180°.

This relationship between local geometry and coupling constant is of great value throughout nuclear magnetic resonance spectroscopy and is particularly valuable for determining backbone torsion angles in protein NMR studies.

External links

• Generalized Karplus calculation of proton-proton coupling constants
• Karplus equations app

Notes and References

1. . 81 . 51 . 37 . 2003-12-22 . Louisa . Dalton . Karplus Equation . 10.1021/cen-v081n036.p037. free .
2. Karplus . Martin . Contact Electron-Spin Coupling of Nuclear Magnetic Moments . 1959 . . 30 . 1 . 11–15 . 10.1063/1.1729860. 1959JChPh..30...11K .
3. Karplus . Martin . Vicinal Proton Coupling in Nuclear Magnetic Resonance . 1963 . . 85 . 18 . 2870–2871 . 10.1021/ja00901a059.