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Based on quantum-mechanical path-integral molecular dynamics simulations the impact of nuclear quantum effects on the vibrational and hydrogen bond dynamics in liquid water is investigated. The instantaneous fluctuations in the frequencies…

软凝聚态物质 · 物理学 2018-09-03 Deepak Ojha , Andres Henao , Thomas D Kühne

Corrections for nuclear quantum effects (NQE) have been calculated for classical molecular dynamics (MD) simulation models of light (H2O), heavy (D2O) and null (H1.28D0.72O) water. New path integral molecular dynamics (PIMD) simulations…

化学物理 · 物理学 2020-11-03 Imre Bakó , Ádám Madarász , László Pusztai

Nuclear quantum effects play critical roles in a variety of molecular processes, especially in systems that contain hydrogen and other light nuclei, such as water. For water at ambient conditions, nuclear quantum effects are often…

化学物理 · 物理学 2023-09-12 Richard C. Remsing

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…

软凝聚态物质 · 物理学 2010-11-05 Scott Habershon , Thomas E. Markland , David E. Manolopoulos

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…

化学物理 · 物理学 2015-04-21 Thomas Spura , Christopher John , Scott Habershon , Thomas D. Kühne

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…

软凝聚态物质 · 物理学 2009-11-13 Joseph A. Morrone , Roberto Car

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…

化学物理 · 物理学 2015-06-19 Lu Wang , Michele Ceriotti , Thomas E. Markland

Vibrational spectroscopy is key for probing the interplay between the structure and dynamics of aqueous systems. In order to map different regions of experimental spectra to the microscopic structure of a system, it is important to combine…

化学物理 · 物理学 2021-08-09 Sam Shepherd , Jinggang Lan , David M. Wilkins , Venkat Kapil

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…

化学物理 · 物理学 2026-05-20 Michael Beerbaum , Julian Heske , Jure Gujt , Thomas D. Kühne

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…

化学物理 · 物理学 2017-02-28 Ondrej Marsalek , Thomas E. Markland

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…

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…

化学物理 · 物理学 2024-12-03 Nore Stolte , János Daru , Harald Forbert , Jörg Behler , Dominik Marx

Vibrational coupling is relevant not only for dissipation of excess energy after chemical reactions but also for elucidating molecular structure and dynamics. It is particularly important for OH stretch vibrational spectra of water, for…

化学物理 · 物理学 2016-11-22 Jan Schaefer , Ellen H. G. Backus , Yuki Nagata , Mischa Bonn

Path-integral molecular dynamics simulations based on density functional theory employing exchange-correlation density functionals capable of treating nonlocal van der Waals (vdW) interactions self-consistently provide a remarkably accurate…

化学物理 · 物理学 2014-02-13 Jeffrey M. McMahon , Miguel A. Morales , Brian Kolb , Timo Thonhauser

We employ classical and ring polymer molecular dynamics simulations to study the effect of nuclear quantum fluctuations on the structure and the water exchange dynamics of aqueous solutions of lithium and fluoride ions. While we obtain…

化学物理 · 物理学 2015-06-23 David M. Wilkins , David E. Manolopoulos , Liem X. Dang

To comprehend the complexities of the ice-water interface, we perform a study that attempts to correlate the altered dynamics of water to its perturbed structure at, and due to, the interface. The deviation from bulk values of structural…

软凝聚态物质 · 物理学 2019-08-02 Saumyak Mukherjee , Sayantan Mondal , Biman Bagchi

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,…

化学物理 · 物理学 2017-12-06 Yair Litman , Davide Donadio , Michele Ceriotti , Mariana Rossi

Hydrogen bonds are of paramount importance in the chemistry of clays, mediating the interaction between the clay surface and water, and for some materials between separate layers. It is well-established that the accuracy of a computational…

化学物理 · 物理学 2022-03-14 Pawan J. K. Kurapothula , Sam Shepherd , David M. Wilkins

Molecules like water have vibrational modes with a zero-point energy well above room temperature. As a consequence, classical molecular dynamics simulations of their liquids largely underestimate the energy of modes with a higher zero-point…

统计力学 · 物理学 2013-05-08 Sriram Ganeshan , Rafael Ramírez , M. V. Fernández-Serra

A computational study of liquid water when the system is coupled with a (model) Fabry-Perot cavity is reported. At this end, the Cavity Born-Oppenheimer Molecular Dynamics approach proposed recently (Li et al., Proc. Nat. Acad. Sci. USA,…

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