J-coupling

Scalar or J-couplings (also called indirect dipole dipole

coupling) are mediated through chemical bonds connecting two spins. It is an indirect interaction between two
nuclear spins which arises from hyperne interactions between the nuclei and local electrons.[1] J-coupling contains information about bond distance and angles. Most
importantly, J-coupling provides information on the connectivity of molecules. In NMR spectroscopy, it is responsible for the appearance of many signals in the NMR
spectra of fairly simple molecules.

pling to quadrupolar nuclei is not observed. Many elements consist of nuclei with nuclear spin and without. In
these cases the observed spectrum is the sum of spectra for each isotopomer. One of the great conveniences
of NMR spectroscopy for organic molecules is that the
many lighter elements are nearly monoisotopic: 1 H, 19 F,
and 31 P each have spin 1/2. 12 C and 16 O have no nuclear
spin.

1.2 Magnitude of J-coupling

For 1 H-1 H coupling, the magnitude of J provides information on the proximity of the coupling partners. Generally speaking 2-bond coupling (i.e. 1 H-C-1 H) is stronger
than three-bond coupling (1 H-C-C-1 H). The magnitude
of the coupling also provides information on the dihedral
angles relating the coupling partners, as described by the
The origin of J-coupling can be visualized by a vector Karplus relationship.
model for a simple molecule such as hydrogen uoride
For heteronuclear coupling, the magnitude of J is related
(HF). In HF, the two nuclei have spin 1/2. Four states
to the nuclear magnetic moments of the coupling partare possible, depending on the relative alignment of the
ners. 19 F, with a high nuclear magnetic moment, gives
H and F nuclear spins with the external magnetic eld.
rise to large coupling to protons. 103 Rh, with a very
The selection rules of NMR spectroscopy dictate that I
small nuclear magnetic moment, gives only small cou= 1, which means that a given photon (in the radio freplings to 1 H. To correct for the eect of the nuclear magquency range) can aect (ip) only one of the two nunetic moment (or equivalently the gyromagnetic ratio ),
clear spins.
reduced coupling constant K is often discussed, where
K = 42 J/(h ). The value of J also has a sign, and
couplings constants of comparable magnitude often have
opposite signs.[2]

Vector model and manifestations

for chemical structure assignments

2 J-coupling Hamiltonian
Energy diagram showing the eects of J-coupling for the
molecule hydrogen uoride.

The Hamiltonian of a molecular system may be taken as:

H = D1 +D2 +D3 .
J-coupling provides three parameters: the multiplicity
(the number of lines), the magnitude of the coupling D1 = electron orbital-orbital, spin-orbital, spin-spin and
electron spin-external eld interactions
(strong, medium, weak), and the sign of the coupling.

1.1

D2 = magnetic interactions between nuclear spin and

electron spin

Multiplicity

D3 = direct interaction of nuclei with each other

The multiplicity provides information on the number of

centers coupled to the signal of interest, and their nuclear spin. For simple systems, as in 1 H-1 H coupling
in NMR spectroscopy, the multiplicity reects the number of adjacent, magnetically nonequivalent protons. Nuclei with spins >1/2, which are called quadrupolar, can
give rise to greater splitting, although in many cases cou-

for a singlet molecular state and frequent molecular collisions, D1 and D3 are almost zero. The full form of Jcoupling interaction between spins I and I on the same
molecule is:
H = 2 Ij Jjk Ik
where J is the j-coupling tensor, a 3x3 real matrix. It
1

REFERENCES

depends on molecular orientation. In isotropic liquid it tween uorine, nitrogen, carbon, silicon and phosphorus
reduces to a number, so called scalar coupling. In 1D atoms.[6][7][8]
NMR, scalar coupling leads to oscillations in FID as well
as splitting of lines in the spectrum.

5 See also
3

Decoupling

By selective radio frequency irradiation, NMR spectra

can be fully or partially decoupled, eliminating or selectively reducing the coupling eect. Carbon-13 NMR are
often run decoupled.

History

In October 1951, E. L. Hahn and D. E. Maxwell reported

a spin echo experiment which indicates the existence of an
interaction between two protons in dichloroacetaldehyde.
In the echo experiment, two short, intense pulses of
radiofrequency magnetic eld are applied to spin ensemble at the nuclear resonance condition and are separated
by time interval of . The echo appears with a given
maximum amplitude at time 2. For each setting of ,
the maximum of the echo signal is measured and plotted as a function of . If the spin ensemble consists of
magnetic moment, a monotonic decay in the echo envelope is obtained. In the Hahn-Maxwell experiment, the
decay was modulated by two frequencies: one frequency
corresponded with the dierence in chemical shift between the two non equivalent spins and a second frequency, J, that was smaller and independent of magnetic
eld strength. (J/2 = 0.7 cycle per second)
Such interaction came as a great surprise. The direct interaction between two magnetic dipoles depends on the
relative position of two nuclei in such a way that when averaged on all various orientation of the molecule it equals
to zero.
In November 1951, N. F. Ramsey and E. M. Purcell proposed a mechanism that explained the observation and
gave rise to an interaction of the form I1 .I2 . The mechanism is the magnetic interaction between each nucleus
and the electron spin of its own atom together with the
exchange coupling of the electron spins with each other.
In the 1990s, direct evidence was found for the presence of J-couplings between magnetically active nuclei on
both sides of the hydrogen bond.[3][4] Initially, it was surprising to observe such couplings across hydrogen bonds
since J-couplings are usually associated with the presence of purely covalent bonds. However, it is now well
established that the H-bond J-couplings follow the same
electron-mediated polarization mechanism as their covalent counterparts.[5]
The spin-spin coupling between nonbonded atoms in
close proximity has sometimes been observed be-

Earths eld NMR

Exclusive correlation spectroscopy (ECOSY)
Magnetic dipole-dipole interaction (dipolar coupling)
Nuclear Magnetic Resonance
Nuclear magnetic resonance spectroscopy of carbohydrates
Nuclear magnetic resonance spectroscopy of nucleic
acids
Nuclear magnetic resonance spectroscopy of proteins
Proton NMR
Relaxation (NMR)
Residual dipolar coupling

6 References
[1] E. L. Hahn and D. E. Maxwell (1952).
Spin
Echo Measurements of Nuclear Spin Coupling in Molecules.
Phys.
Rev.
88 (5):
10701084.
Bibcode:1952PhRv...88.1070H.
doi:10.1103/PhysRev.88.1070.
[2] Pregosin, P. S.; Rueegger, H. Nuclear magnetic resonance spectroscopy McCleverty, Jon A.; Meyer, Thomas
J., Eds., Comprehensive Coordination Chemistry II
(2004), 2, 1-35. doi:10.1016/B0-08-043748-6/01061-6
[3] P. Blake, B. Lee, M. Summers, M. Adams, J.B. Park, Z. Zhou and A. Bax (1992). Quantitative measurement of small through-hydrogen-bond and
'through-space' 1 H-113 Cd and 1 H-199 Hg J couplings
in metal-substituted rubredoxin from Pyrococcus furiosus. Journal of Biomolecular NMR 2 (5): 527533.
doi:10.1007/BF02192814.
[4] P. R. Blake, J. B. Park, M. W. W. Adams and M. F.
Summers (1992). Novel observation of NH--S(Cys)
hydrogen-bond-mediated scalar coupling in cadmium113 substituted rubredoxin from Pyrococcus furiosus.
J. Am.
Chem.
Soc.
114 (12): 49314933.
doi:10.1021/ja00038a084.
[5] Andrew J. Dingley, Florence Cordier and Stephan Grzesiek (2001). An introduction to hydrogen bond scalar
couplings. Concepts in Magnetic Resonance 13 (2): 103
doi:10.1002/1099-0534(2001)13:2<103::AID127.
CMR1001>3.0.CO;2-M.

[6] Mallory, F. B. et al. (2000). Nuclear SpinSpin

Coupling via Nonbonded Interactions. 8. 1 The Distance Dependence of Through-Space FluorineFluorine
Coupling. J. Am. Chem. Soc 122: 41084116.
doi:10.1021/ja993032z.
[7] Zong, J.; Mague, J. T.; Kraml, C. M.; Pascal Jr, R. A.
(2013). A Congested in, in-Diphosphine. Organic Letters 15 (9): 21792181. doi:10.1021/ol400728m.
[8] Zong, J.; Mague, J. T.; Welch, E. C.; Eckert, I. M.; Pascal
Jr, R. A. (2013). Sterically congested macrobicycles with
heteroatomic bridgehead functionality. Tetrahedron 69
(48): 1031610321. doi:10.1016/j.tet.2013.10.018.

Further reading
H. S. Gutowsky, D. W. McCall, C. P. Slichter
(1951).
Coupling among Nuclear Magnetic
Dipoles in Molecules.
Physical Review 84
(3): 58990.
Bibcode:1951PhRv...84..589G.
doi:10.1103/PhysRev.84.589.2.
E. L. Hahn and D. E. Maxwell (1951). Chemical
Shift and Field Independent Frequency Modulation
of the Spin Echo Envelope. Physical Review 84
(6): 12461247. Bibcode:1951PhRv...84.1246H.
doi:10.1103/PhysRev.84.1246.
N. F. Ramsey and E. M. Purcell (1952).
Interactions between Nuclear Spins in
Molecules.
Physical Review 85 (1):
143144.
Bibcode:1952PhRv...85..143R.
doi:10.1103/PhysRev.85.143.

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