Xin-Zheng Li

Quantum nature of the hydrogen bond

Hydrogen bonds are weak, generally intermolecular bonds, which hold much of soft matter together as well as the condensed phases of water, network liquids, and many ferroelectric crystals. The small mass of hydrogen means that they are inherently quantum mechanical in nature, and effects such as zero-point motion and tunneling must be considered, though all too often these effects are not considered. As a prominent example, a clear picture for the impact of quantum nuclear effects on the strength of hydrogen bonds and consequently the structure of hydrogen bonded systems is still absent. Here, we report ab initio path integral molecular dynamics studies on the quantum nature of the hydrogen bond. Through a systematic examination of a wide range of hydrogen bonded systems we show that quantum nuclear effects weaken weak hydrogen bonds but strengthen relatively strong ones. This simple correlation arises from a competition between anharmonic intermolecular bond bending and intramolecular bond stretching. A simple rule of thumb is provided that enables predictions to be made for hydrogen bonded materials in general with merely classical knowledge (such as hydrogen bond strength or hydrogen bond length). Our work rationalizes the influence of quantum nuclear effects, which can result in either weakening or strengthening of the hydrogen bonds, and the corresponding structures, across a broad range of hydrogen bonded materials. Furthermore, it highlights the need to allow flexible molecules when anharmonic potentials are used in force field-based studies of quantum nuclear effects.

Real-space imaging of interfacial water with submolecular resolution

Water/solid interfaces are vital to our daily lives and are also a central theme across an incredibly wide range of scientific disciplines. Resolving the internal structure, that is, the O-H directionality, of water molecules adsorbed on solid surfaces has been one of the key issues of water science yet it remains challenging. Using a low-temperature scanning tunnelling microscope, we report submolecular-resolution imaging of individual water monomers and tetramers on NaCl(001) films supported by a Au(111) substrate at 5 K. The frontier molecular orbitals of adsorbed water were directly visualized, which allowed discrimination of the orientation of the monomers and the hydrogen-bond directionality of the tetramers in real space. Comparison with ab initio density functional theory calculations reveals that the ability to access the orbital structures of water stems from the electronic decoupling effect provided by the NaCl films and the precisely tunable tip-water coupling.

Nuclear quantum effects of hydrogen bonds probed by tip-enhanced inelastic electron tunneling

Quantum effects in single hydrogen bonds Hydrogen bonds are a combination of electrostatics with a nuclear quantum contribution arising from the light mass of hydrogen nuclei. However, the quantum states of hydrogen nuclei are extremely sensitive to coupling with local environments, and these effects are broadened and averaged with conventional spectroscopic or diffraction techniques. Guo et al. show that quantum effects change the strength of individual hydrogen bonds in water layers adsorbed on a salt surface. These effects are revealed in inelastic tunneling spectra obtained with a chlorine-terminated scanning tunneling microscope tip. Science, this issue p. 321 Quantum effects in water hydrogen bonding are revealed with a chlorine-terminated scanning tunneling microscope tip. We report the quantitative assessment of nuclear quantum effects on the strength of a single hydrogen bond formed at a water-salt interface, using tip-enhanced inelastic electron tunneling spectroscopy based on a scanning tunneling microscope. The inelastic scattering cross section was resonantly enhanced by “gating” the frontier orbitals of water via a chlorine-terminated tip, so the hydrogen-bonding strength can be determined with high accuracy from the red shift in the oxygen-hydrogen stretching frequency of water. Isotopic substitution experiments combined with quantum simulations reveal that the anharmonic quantum fluctuations of hydrogen nuclei weaken the weak hydrogen bonds and strengthen the relatively strong ones. However, this trend can be completely reversed when a hydrogen bond is strongly coupled to the polar atomic sites of the surface.

Quantum simulation of low-temperature metallic liquid hydrogen

The melting temperature of solid hydrogen drops with pressure above ~65 GPa, suggesting that a liquid state might exist at low temperatures. It has also been suggested that this low-temperature liquid state might be non-molecular and metallic, although evidence for such behaviour is lacking. Here we report results for hydrogen at high pressures using ab initio methods, which include a description of the quantum motion of the protons. We determine the melting temperature as a function of pressure and find an atomic solid phase from 500 to 800 GPa, which melts at <200 K. Beyond this and up to 1,200 GPa, a metallic atomic liquid is stable at temperatures as low as 50 K. The quantum motion of the protons is critical to the low melting temperature reported, as simulations with classical nuclei lead to considerably higher melting temperatures of ~300 K across the entire pressure range considered.

Direct observation of ordered configurations of hydrogen adatoms on graphene.

Ordered configurations of hydrogen adatoms on graphene have long been proposed, calculated, and searched for. Here, we report direct observation of several ordered configurations of H adatoms on graphene by scanning tunneling microscopy. On the top side of the graphene plane, H atoms in the configurations appear to stick to carbon atoms in the same sublattice. Scanning tunneling spectroscopy measurements revealed a substantial gap in the local density of states in H-contained regions as well as in-gap states below the conduction band due to the incompleteness of H ordering. These findings can be well explained by density functional theory calculations based on double-sided H configurations. In addition, factors that may influence H ordering are discussed.

An unconventional bilayer ice structure on a NaCl(001) film

Water-solid interactions are of broad importance both in nature and technology. The hexagonal bilayer model based on the Bernal-Fowler-Pauling ice rules has been widely adopted to describe water structuring at interfaces. Using a cryogenic scanning tunnelling microscope, here we report a new type of two-dimensional ice-like bilayer structure built from cyclic water tetramers on an insulating NaCl(001) film, which is completely beyond this conventional bilayer picture. A novel bridging mechanism allows the interconnection of water tetramers to form chains, flakes and eventually a two-dimensional extended ice bilayer containing a regular array of Bjerrum D-type defects. Ab initio density functional theory calculations substantiate this bridging growth mode and reveal a striking proton-disordered ice structure. The formation of the periodic Bjerrum defects with unusually high density may have a crucial role as H donor sites in directing multilayer ice growth and in catalysing heterogeneous chemical reactions on water-coated salt surfaces.

Impact of widely used approximations to the G0W0 method: an all-electron perspective

Focusing on the fundamental band gaps in Si, diamond, BN, LiF, AlP, NaCl, CaSe and GaAs, and the semicore d-state binding energies in ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe and GaN, we study the differences between the all-electron (AE) and the pseudopotential (PP)-based G0W0 method. Leaving aside issues related to the choice of PPs within PP-G0W0, we analyze in detail the well-known discrepancies between AE-G0W0 and PP-G0W0 band gaps by separately addressing the approximations underlying PP-G0W0, i.e. the frozen-core approximation, the core-valence partitioning and the use of pseudo-wavefunctions. The largest differences, of the order of eV, appear in the exchange part of the self-energy and the exchange-correlation potential due to the core-valence partitioning. These differences cancel each other and, in doing so, make the final core-valence partitioning effect on the band gaps controllable when the semicore states are treated as valence states. This cancelation, however, is incomplete for semicore d-state binding energies, due to the strong interaction between these semicore states and the deep core. From our comprehensive analysis, we conclude that reliably describing the many-body interactions at the G0W0 level and providing benchmark results require an AE treatment.

Inverse Temperature Dependence of Nuclear Quantum Effects in DNA Base Pairs

Despite the inherently quantum mechanical nature of hydrogen bonding, it is unclear how nuclear quantum effects (NQEs) alter the strengths of hydrogen bonds. With this in mind, we use ab initio path integral molecular dynamics to determine the absolute contribution of NQEs to the binding in DNA base pair complexes, arguably the most important hydrogen-bonded systems of all. We find that depending on the temperature, NQEs can either strengthen or weaken the binding within the hydrogen-bonded complexes. As a somewhat counterintuitive consequence, NQEs can have a smaller impact on hydrogen bond strengths at cryogenic temperatures than at room temperature. We rationalize this in terms of a competition of NQEs between low-frequency and high-frequency vibrational modes. Extending this idea, we also propose a simple model to predict the temperature dependence of NQEs on hydrogen bond strengths in general.

Systematic investigation on topological properties of layered GaS and GaSe under strain

The topological properties of layered β-GaS and ε-GaSe under strain are systematically investigated by ab initio calculations with the electronic exchange-correlation interactions treated beyond the generalized gradient approximation (GGA). Based on the GW method and the Tran-Blaha modified Becke-Johnson potential approach, we find that while ε-GaSe can be strain-engineered to become a topological insulator, β-GaS remains a trivial one even under strong strain, which is different from the prediction based on GGA. The reliability of the fixed volume assumption rooted in nearly all the previous calculations is discussed. By comparing to strain calculations with optimized inter-layer distance, we find that the fixed volume assumption is qualitatively valid for β-GaS and ε-GaSe, but there are quantitative differences between the results from the fixed volume treatment and those from more realistic treatments. This work indicates that it is risky to use theoretical approaches like GGA that suffer from the band gap problem to address physical properties, including, in particular, the topological nature of band structures, for which the band gap plays a crucial role. In the latter case, careful calibration against more reliable methods like the GW approach is strongly recommended.

On the room-temperature phase diagram of high pressure hydrogen: An ab initio molecular dynamics perspective and a diffusion Monte Carlo study

The finite-temperature phase diagram of hydrogen in the region of phase IV and its neighborhood was studied using the ab initio molecular dynamics (MD) and the ab initio path-integral molecular dynamics (PIMD). The electronic structures were analyzed using the density-functional theory (DFT), the random-phase approximation, and the diffusion Monte Carlo (DMC) methods. Taking the state-of-the-art DMC results as benchmark, comparisons of the energy differences between structures generated from the MD and PIMD simulations, with molecular and dissociated hydrogens, respectively, in the weak molecular layers of phase IV, indicate that standard functionals in DFT tend to underestimate the dissociation barrier of the weak molecular layers in this mixed phase. Because of this underestimation, inclusion of the quantum nuclear effects (QNEs) in PIMD using electronic structures generated with these functionals leads to artificially dissociated hydrogen layers in phase IV and an error compensation between the neglect of QNEs and the deficiencies of these functionals in standard ab initio MD simulations exists. This analysis partly rationalizes why earlier ab initio MD simulations complement so well the experimental observations. The temperature and pressure dependencies for the stability of phase IV were also studied in the end and compared with earlier results.