Anomalously supercooled H2-D2 mixtures flowing inside a carbon nano tube.

H2 and D2 molecules condensed in a carbon nano tube (CNT) and their nonequilibrium flow through nano pores offer a key test to reveal mass molecular transport and separation of purely isotopic molecules that possess the same electronic potential but a two-times difference in mass inducing differently enhanced nuclear quantum effects (NQEs) such as nuclear delocalization and zero-point energy. Taking advantage of the non-empirical quantum molecular dynamics method developed for condensed H2-D2 molecules that can describe various kinds of condensed phases and thermodynamic states including uneven density and a shear flow, we investigated condensed isotopic H2-D2 mixtures flowing inside nanoscale adsorbable CNTs. We found that, in any mixture, the more delocalized H2 molecules are more supercooled than the less delocalized D2 molecules in a two-dimensional liquid film adsorbed around the CNT well, and that the stronger supercooling of the H2 molecules than the D2 molecules in an equilibrium state becomes more enhanced under the nonequilibrium flow due to the isotope-dependent flow-induced condensation, demonstrating the anomalous condensed-phase quantum sieving under the nonequilibrium flow and its dependence on the mixing ratio and temperature. The differently enhanced NQEs of the purely isotopic molecules essentially influence the condensed adsorption and their flows occurring in the nanoscale CNT, which should be distinguished from a dilute gas adsorption. The predicted properties and obtained physical insights in this paper will help in experimentally controlling condensed H2-D2 mixtures, and open a new strategy and innovative design of nanoporous materials for adsorptive separation of condensed-phase mixtures under a nonequilibrium flow not of a dilute gas mixture in an equilibrium state.

Flow-Induced Autonomic Ordering of Hydrogen Molecules under a Non-Equilibrium Flow.

A non-equilibrium molecular flow through a carbon nanotube (CNT) serves as a key system for revealing molecular transport and establishing nanofluidics. It has been challenging to simulate a non-equilibrium flow of hydrogen molecules exhibiting strong nuclear quantumness. Taking advantage of the quantum molecular dynamics method that can calculate real-time trajectories of hydrogen molecules even under a non-equilibrium flow, we found that the non-equilibrium flow makes hydrogen molecules more condensed and accelerates their adsorption near a CNT surface, letting the molecules flow more smoothly by propagating velocity momenta more efficiently along the CNT axis and by suppressing transverse molecular dynamics on the CNT cross section. Such flow-induced autonomic ordering indicates the importance of monitoring and investigating dynamics and adsorption of hydrogen molecules under a non-equilibrium circumstance as well as in a quiet equilibrium state, opening a new strategy for efficient hydrogen liquefaction and storage.

Distinct molecular dynamics dividing liquid-like and gas-like supercritical hydrogens.

Understanding how a supercritical fluid is related to normal liquid and gas and separating it into liquid-like and gas-like regions are of fundamental and practical importance. Despite the usefulness of hydrogen storage, molecular dynamics images on supercritical hydrogens exhibiting strong nuclear quantum effects are scarce. Taking advantage of the non-empirical ab initio molecular dynamics method for hydrogen molecules, we found that, while radial distribution functions and diffusion show a monotonic change along the density, van Hove time correlation functions and intramolecular properties such as bond length and vibrational frequency exhibit the anomalous order crossing the Widom line. By demonstrating that the anomalous order stemmed from the largest deviations between liquid-like and gas-like solvations formed around the Widom line, we concluded that this supercritical fluid is a mixture of liquid and gas possessing heterogeneity. The obtained physical insights can be an index to monitor the supercriticality and to identify distinct liquid-like and gas-like supercritical fluids.

Decelerated Liquid Dynamics Induced by Component-Dependent Supercooling in Hydrogen and Deuterium Quantum Mixtures.

Isotopic mixtures of p-H2 and o-D2 molecules have been an attractive binary system because they include two kinds of purely isotopic molecules which possess the same electronic potential but the twice different mass inducing differently pronounced nuclear quantum effects (NQEs). Accessing details of structures and dynamics in such quantum mixtures combining complex molecular dynamics with NQEs of different strengths remains a challenging problem. Taking advantage of the nonempirical molecular dynamics method which describes p-H2 and o-D2 molecules, we found that the liquid dynamics slows down at a specific mixing ratio, which can be connected to the observed anomalous slowdown of crystallization in the quantum mixtures. We attributed the decelerated dynamics to the component-dependent supercooling of p-H2 taking place in the mixtures, demonstrating that there is an optimal mixing ratio to hinder crystallization. The obtained physical insights will help in experimentally controlling and achieving unknown quantum mixtures including superfluid.

Isotopic Effects on Intermolecular and Intramolecular Structure and Dynamics in Hydrogen, Deuterium, and Tritium Liquids: Normal Liquid and Weakly and Strongly Cooled Liquids.

Differences in properties such as phase-transition temperature and transport coefficients among liquids of different isotopic compositions, hydrogen, deuterium, and tritium, should originate from their differently pronounced nuclear quantum effects (NQEs) rather than from any subtle difference in the electronic interaction potentials. Accurate and efficient determination of structural and dynamical isotopic effects in the quantum liquids still remains as one of the challenging problems in condensed-phase physics. With a recently developed nonempirical real-time molecular dynamics method which describes nonspherical molecules with the NQEs, we computationally realized and investigated dynamical and quantum isotopic effects of not only traditionally studied isotopes, hydrogen, and deuterium but also a lesser known radioisotope, tritium, in broad thermodynamic conditions from normal liquid to weakly and strongly cooled liquids, which have been hindered by rapid crystallization in spite of numerous experimental attempts at supercooling. Reproducing the previously reported experimental isotope dependence on the bond length and vibrational frequencies of hydrogen, deuterium, and tritium liquids, we further demonstrate that distinctive isotope effects appear in their intermolecular and intramolecular structure and dynamics not only at lower temperature but also at higher temperature, which none has so far been able to obtain quantitative results for realistic systems. Rationalization of their physical origins and the obtained physical insights will help future experimental searching and monitoring intermolecular and intramolecular dynamics and structures of these isotopes not only in normal liquid but also in supercooled liquid.