Ученые из Токио доказали, что симметрия кристаллической решетки управляет квантовым туннелированием водорода

The quantum tunnelling of hydrogen atoms plays a central role in many physical, chemical and biological process, but a practical means of controlling it has proved elusive. Researchers from the University of Tokyo, Japan have now demonstrated that the way hydrogen permeates through a material depends on the degree of symmetry in the material’s crystal structure. By controlling this symmetry, scientists could therefore gain control over hydrogen’s ability to tunnel, potentially leading to safer and more efficient media for storing this industrially important clean-burning fuel. “We found that hydrogen undergoes pronounced quantum tunnelling in a highly symmetric crystal environment, whereas the tunnelling is strongly suppressed when the symmetry is lowered,” explains Katsuyuki Fukutani, who led the research together with colleagues Takahiro Ozawa and Sudhansu Sekhar Das. “This is particularly exciting because it identifies crystal symmetry as a fundamental principle for controlling the quantum behaviour of hydrogen in materials, opening new possibilities for tailoring hydrogen transport.” A model hydrogen-storage material The researchers, who work at Tokyo’s Institute of Industrial Science, obtained their results by studying how hydrogen atoms move through a model hydrogen-storage material, vanadium, at low temperatures. To do this, they combined two complementary techniques. The first is called nuclear reaction analysis and it measures the hydrogen’s depth distribution directly with high resolution. The second involves measuring electrical resistance, which sensitively monitors how the hydrogen redistributes itself over time. These measurements revealed that at temperatures of around 70 K, hydrogen atoms begin to migrate through vanadium’s crystal lattice, hopping between its interstitial spaces. At low hydrogen concentrations, this hopping occurs within a highly symmetric structure known as α-phase vanadium, and the hydrogen atoms easily tunnel between neighbouring lattice sites. At higher hydrogen concentrations, however, vanadium’s crystal lattice distorts, forming a β-phase. Under these conditions, the hydrogen atoms must overcome an energy barrier (of 148 meV in this case) before they can tunnel to neighbouring sites. Quantum tunnelling or classical thermal activation? Based on changes to vanadium’s electrical resistance, the researchers were able to calculate the diffusion coefficient of hydrogen over a wide range of temperatures, including those for which quantum tunnelling is important. They then interpreted these results using quantum-mechanical calculations of hydrogen motion, which revealed that the crystal symmetry determines whether hydrogen moves by quantum tunnelling or by classical thermal activation. They found that in the α-phase, hydrogen’s ground states are delocalized over tetrahedral sites thanks to tunnelling. In the β-phase, in contrast, the uniaxial strain produced by the distortion of the crystal lattice leads the quantum states of the hydrogen atoms to localize around certain (Oz) sites in the material. Hydrogen is the lightest element, so Fukutani says it’s not surprising that it exhibits pronounced quantum behaviour. However, while quantum tunnelling had long been assumed to play an important role in hydrogen diffusion, it was difficult to obtain direct experimental evidence for it because we cannot easily observe hydrogen inside materials using conventional techniques. “We wanted to clarify how hydrogen actually behaves in the quantum regime and identify the factors that control its tunnelling,” he explains. New possibilities for controlling hydrogen permeation and storage “Our findings suggest that hydrogen transport can be controlled by tuning quantum tunnelling through crystal symmetry — for example by applying external strain,” he adds. “This capability opens up new possibilities for controlling hydrogen permeation, storage and even catalytic reactions.” Superfluid phase spotted in molecular hydrogen for the first time More broadly, Fukutani says the team’s work establishes crystal symmetry as a new design principle for tailoring quantum hydrogen behaviour in functional materials. The Tokyo researchers now plan to extend their work to a wider range of hydrogen storage media, including metal alloys and oxide materials. “Ultimately, we hope to establish a universal framework describing how local atomic structure and crystal symmetry govern the quantum behaviour of hydrogen,” Fukutani tells Physics World. They report their present work in Nature Communications.