相关论文: Quantum kinetic energy and isotope fractionation i…
When two phases of water are at equilibrium, the ratio of hydrogen isotopes in each is slightly altered due to their different phase affinities. This isotopic fractionation process can be utilized to analyze water's movement in the world's…
We have applied path integral simulations, in combination with new ab initio based water potentials, to investigate nuclear quantum effects in liquid water. Because direct ab initio path integral simulations are computationally expensive, a…
Nuclear quantum effects, such as zero-point energy and tunneling, cause significant changes to the structure and dynamics of hydrogen bonded systems such as liquid water. However, due to the current inability to simulate liquid water using…
Water molecules adsorbed on inorganic substrates play an important role in several technological applications. In the presence of light atoms in adsorbates, nuclear quantum effects (NQE) influence properties of these systems. In this work,…
Understanding the reactivity and spectroscopy of aqueous solutions at the atomistic level is crucial for the elucidation and design of chemical processes. However, the simulation of these systems requires addressing the formidable…
The isotope effect in the melting temperature of ice Ih has been studied by free energy calculations within the path integral formulation of statistical mechanics. Free energy differences between isotopes are related to the dependence of…
In this study we investigate the nuclear quantum effects (NQEs) on the acidity constant (pKA) of liquid water isotopologues at the ambient condition by path integral molecular dynamics (PIMD) simulations. We compared simulations using a…
Supercooled water is expected to exhibit a liquid--liquid phase transition between low- and high-density liquid states, possibly terminating in a liquid--liquid critical point in the experimentally difficult no man's land. Because the…
The electronic properties and optical response of ice and water are intricately shaped by their molecular structure, including the quantum mechanical nature of hydrogen atoms. In spite of numerous studies appeared over decades, a…
In this work, a path integral Car-Parrinello molecular dynamics simulation of liquid water is performed. It is found that the inclusion of nuclear quantum effects systematically improves the agreement of first principles simulations of…
Isotopic substitution, which can be realized both in experiment and computer simulations, is a direct approach to assess the role of nuclear quantum effects on the structure and dynamics of matter. Yet, the impact of nuclear quantum effects…
Light nuclei at room temperature and below exhibit a kinetic energy which significantly deviates from the predictions of classical statistical mechanics. This quantum kinetic energy is responsible for a wide variety of isotope effects of…
Numerous studies have identified large quantum mechanical effects in the dynamics of liquid water. In this paper, we suggest that these effects may have been overestimated due to the use of rigid water models and flexible models in which…
Nuclear quantum effects (NQEs) on the structures and transport properties of dense liquid hydrogen at densities of 10-100 g/cm3 and temperatures of 0.1-1 eV are fully assessed using \textit{ab initio} path-integral molecular dynamics…
Even at room temperature, quantum mechanics plays a major role in determining the quantitative behaviour of light nuclei, changing significantly the values of physical properties such as the heat capacity. However, other observables appear…
The kinetic energy of H and O nuclei has been studied by path integral molecular dynamics simulations of ice Ih and water at ambient pressure. The simulations were performed by using the q-TIP4P/F model, a point charge empirical potential…
With a view to a better understanding of the influence of atomic quantum delocalisation effects on the phase behaviour of water, path integral simulations have been undertaken for almost all of the known ice phases using the TIP4P/2005…
A comprehensive microscopic understanding of ambient liquid water is a major challenge for $ab$ $initio$ simulations as it simultaneously requires an accurate quantum mechanical description of the underlying potential energy surface (PES)…
The shift in chemical equilibria due to isotope substitution is often exploited to gain insight into a wide variety of chemical and physical processes. It is a purely quantum mechanical effect, which can be computed exactly using…
Recent experiments have confirmed the importance of nuclear quantum effects even in large biomolecules at physiological temperature. Here we describe how the path integral formalism can be used to describe rigorously the nuclear quantum…