Nuclear quadrupole resonance

Nuclear quadrupole resonance spectroscopy or NQR is a chemical analysis technique related to nuclear magnetic resonance (NMR).^[1] Unlike NMR, NQR transitions of nuclei can be detected in the absence of a magnetic field, and for this reason NQR spectroscopy is referred to as "zero Field NMR." The NQR resonance is mediated by the interaction of the electric field gradient (EFG) with the quadrupole moment of the nuclear charge distribution. Because the EFG at the location of a nucleus in a given substance is determined primarily by the valence electrons involved in the particular bond with other nearby nuclei, the NQR frequency at which transitions occur is unique for a given substance. A particular NQR frequency in a compound or crystal is proportional to the product of the nuclear quadrupole moment, a property of the nucleus, and the EFG in the neighborhood of the nucleus. It is this product which is termed the nuclear quadrupole coupling constant for a given isotope in a material and can be found in tables of known NQR transitions.

Principle

In NMR, nuclei with spin ≥ 1/2 have a magnetic dipole moment so that their energies are split by a magnetic field, allowing resonance absorption of energy related to the difference between the ground state energy and the excited state. In NQR, on the other hand, nuclei with spin ≥ 1, such as ¹⁴N, ¹⁷O, ³⁵Cl and ⁶³Cu, also have an electric quadrupole moment so that their energies are split by an electric field gradient, created by the electronic bonds in the local environment. This quadrupole moment is associated with non-spherical charge distribution, and is a measure of flatness or oblateness. Since unlike NMR, NQR is done in an environment without a static (or DC) magnetic field, it is sometimes called "zero field NMR". Many NQR transition frequencies depend strongly upon temperature.

Any nucleus with more than one unpaired nuclear particle (protons or neutrons) will have a charge distribution which results in an electric quadrupole moment. Allowed nuclear energy levels are shifted unequally due to the interaction of the nuclear charge with an electric field gradient supplied by the non-uniform distribution electron density (e.g. from bonding electrons) and/or surrounding ions. As in the case of NMR, irradiation of the nucleus with a burst of RF electromagnetic radiation, if of a particular frequency, results in absorption of some energy by the nucleus which can be viewed as a perturbation of the quadrupole energy level. Unlike the NMR case, NQR absorption takes place in the absence of an external magnetic field. Application of an external static field to a quadrupolar nucleus splits the quadrupole levels by the energy predicted from the Zeeman interaction . The technique is very sensitive to the nature and symmetry of the bonding around the nucleus. The energy level shifts are much larger than the chemical shifts measured in NMR. Due to symmetry, the shifts become averaged to zero in the liquid phase, so NQR spectra can only be measured for solids.

Applications

There are several research groups around the world currently working on ways to use NQR to detect explosives. Units designed to detect landmines^[2] and explosives concealed in luggage have been tested. A detection system consists of a radio frequency (RF) power source, a coil to produce the magnetic excitation field and a detector circuit which monitors for a RF NQR response coming from the explosive component of the object.

A fake device known as the ADE 651 claimed to exploit NQR to detect explosives but in fact could do no such thing. Nonetheless, the device was successfully sold for millions to dozens of countries, including the government of Iraq.

Another practical use for NQR is measuring the water/gas/oil coming out of an oil well in realtime. This particular technique allows local or remote monitoring of the extraction process, calculation of the well's remaining capacity and the water/detergents ratio the input pump must send to efficiently extract oil.

Due to the strong temperature dependence of the NQR frequency, it can be used as a precise temperature sensor with resolution on the order of 10⁻⁴°C.^[3]

References