“As it happens,” Budker says, “there are already methods for overcoming small polarization and low detection efficiency, the first two objections to low- or zero-field NMR. By bringing these separate methods together, we can tackle the third objection – no chemical shift – as well. Zero-field NMR may not be such a bad idea after all.”

Net spin orientation can be increased in various ways, collectively known as hyperpolarization. One way to hyperpolarize a sample of hydrogen gas is to change the proportions of parahydrogen and orthohydrogen in it. Like most gases, at normal temperature and pressure each hydrogen molecule consists of two atoms bound together. If the spins of the proton nuclei point in the same direction, it’s orthohydrogen. If the spins point in opposite directions, it’s parahydrogen.

By the mathematics of quantum mechanics, adding up the spin states of the two protons and two electrons in a hydrogen molecule equals three ways for orthohydrogen to reach spin one; parahydrogen can only be spin zero, however. Thus orthohydrogen molecules normally account for three-quarters of hydrogen gas and parahydrogen only one-quarter.

Parahydrogen can be enhanced to 50 percent or even 100 percent using very low temperatures, although the right catalyst must be added or the conversion could take days if not weeks. Then, by chemically reacting spin-zero parahydrogen molecules with an initial chemical, net polarization of the product of the hydrogenation may end up highly polarized. This hyperpolarization can be extended not only to the parts of the molecule directly reacting with the hydrogen, but even to the far corners of large molecules. The Pinenuts, who devised many of the techniques, are masters of parahydrogen production and its hyperpolarization chemistry.

“With a high proportion of parahydrogen you get a terrific degree of polarization,” says Ledbetter. “The catch is, it’s spin zero. It doesn’t have a magnetic moment, so it doesn’t give you a signal! But all is not lost….”

And now for the magic

In low magnetic fields, increasing detection efficiency requires a very different approach, using detectors called magnetometers. In early low-field experiments, magnetometers called SQUID were used (superconducting quantum interference devices). Although exquisitely sensitive, SQUID, like the big magnets used in high-field NMR, must be cryogenically cooled to low temperatures.

Optical-atomic magnetometers are based on a different principle – one that, curiously, is something like NMR in reverse, except that optical-atomic magnetometers measure whole atoms, not just nuclei. Here, an external magnetic field is measured by measuring the spin of the atoms inside the magnetometer’s own vapor cell, typically a thin gas of an alkali metal such as potassium or rubidium. Their spin is influenced by polarizing the atoms with laser light; if there’s even a weak external field, they begin to precess. A second laser beam probes how much they’re precessing and thus just how strong the external field is.

Budker’s group has brought optical-atomic magnetometry to a high pitch by such techniques as extending the “relaxation time,” the time before the polarized vapor loses its polarization. In previous collaborations, the Pines and Budker groups have used magnetometers with NMR and MRI to image the flow of water using only the Earth’s magnetic field or no field at all, to detect hyperpolarized xenon gas (but without analyzing chemical states), and in other applications. The next frontier is chemical analysis.

“No matter how sensitive your detector or how polarized your samples, you can’t detect chemical shifts in a zero field,” Budker says. “But there has always been another signal in NMR that can be used for chemical analysis – it’s just that it is usually so weak compared to chemical shifts, it has been the poor relative in the NMR family. It’s called J-coupling.”

Discovered in 1950 by the NMR pioneer Erwin Hahn and his graduate student, Donald Maxwell, J-coupling provides an interaction pathway between two protons (or other nuclei with spin), which is mediated by their associated electrons. The signature frequencies of these interactions, appearing in the NMR spectrum, can be used to determine the angle between chemical bonds and distances between the nuclei.

“You can even tell how many bonds separate the two spins,” Ledbetter says. “J-coupling reveals all that information.”

The resulting signals are highly specific and indicate just what chemical species is being observed. Moreover, as Hahn saw right away, while the signal can be modified by external magnetic fields, it does not vanish in their absence.