skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Nuclear Quantum Effects in Water and Aqueous Systems: Experiment, Theory, and Current Challenges

Authors:
 [1];  [2];  [3];  [4];  [2];  [5];  [6]
  1. Laboratory of Computational Science and Modeling, Institute of Materials, École Polytechnique Fédérale de Lausanne, 1015 Lausanne, Switzerland
  2. Thomas Young Centre, London Centre for Nanotechnology and Department of Physics and Astronomy, University College London, London WC1E 6BT, United Kingdom
  3. Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4, Canada
  4. School of Mathematics and Physics, University of Queensland, Brisbane, 4072 Queensland Australia
  5. Lawrence Livermore National Laboratory, Livermore, California 94550, United States
  6. Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, California 94305, United States
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1367996
Report Number(s):
LLNL-JRNL-677797
Journal ID: ISSN 0009-2665
Grant/Contract Number:
AC52-07NA27344
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemical Reviews
Additional Journal Information:
Journal Volume: 116; Journal Issue: 13; Journal ID: ISSN 0009-2665
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Ceriotti, Michele, Fang, Wei, Kusalik, Peter G., McKenzie, Ross H., Michaelides, Angelos, Morales, Miguel A., and Markland, Thomas E. Nuclear Quantum Effects in Water and Aqueous Systems: Experiment, Theory, and Current Challenges. United States: N. p., 2016. Web. doi:10.1021/acs.chemrev.5b00674.
Ceriotti, Michele, Fang, Wei, Kusalik, Peter G., McKenzie, Ross H., Michaelides, Angelos, Morales, Miguel A., & Markland, Thomas E. Nuclear Quantum Effects in Water and Aqueous Systems: Experiment, Theory, and Current Challenges. United States. doi:10.1021/acs.chemrev.5b00674.
Ceriotti, Michele, Fang, Wei, Kusalik, Peter G., McKenzie, Ross H., Michaelides, Angelos, Morales, Miguel A., and Markland, Thomas E. 2016. "Nuclear Quantum Effects in Water and Aqueous Systems: Experiment, Theory, and Current Challenges". United States. doi:10.1021/acs.chemrev.5b00674. https://www.osti.gov/servlets/purl/1367996.
@article{osti_1367996,
title = {Nuclear Quantum Effects in Water and Aqueous Systems: Experiment, Theory, and Current Challenges},
author = {Ceriotti, Michele and Fang, Wei and Kusalik, Peter G. and McKenzie, Ross H. and Michaelides, Angelos and Morales, Miguel A. and Markland, Thomas E.},
abstractNote = {},
doi = {10.1021/acs.chemrev.5b00674},
journal = {Chemical Reviews},
number = 13,
volume = 116,
place = {United States},
year = 2016,
month = 4
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 58works
Citation information provided by
Web of Science

Save / Share:
  • Nuclear quantum effects influence the structure and dynamics of hydrogen bonded systems, such as water, which impacts their observed properties with widely varying magnitudes. This review highlights the recent significant developments in the experiment, theory and simulation of nuclear quantum effects in water. Novel experimental techniques, such as deep inelastic neutron scattering, now provide a detailed view of the role of nuclear quantum effects in water’s properties. These have been combined with theoretical developments such as the introduction of the competing quantum effects principle that allows the subtle interplay of water’s quantum effects and their manifestation in experimental observables tomore » be explained. We discuss how this principle has recently been used to explain the apparent dichotomy in water’s isotope effects, which can range from very large to almost nonexistent depending on the property and conditions. We then review the latest major developments in simulation algorithms and theory that have enabled the efficient inclusion of nuclear quantum effects in molecular simulations, permitting their combination with on-the-fly evaluation of the potential energy surface using electronic structure theory. Finally, we identify current challenges and future opportunities in the area.« less
  • Henry's law constants, K/sub H/ = K/sup 0/ + K/sub 1/X, have been measured as a function of concentration for the water-rich and benzene-rich solutions C/sub 6/H/sub 6//H/sub 2/O and C/sub 6/H/sub 6//D/sub 2/O and for the water-rich solutions C/sub 6/D/sub 6//H/sub 2/O and C/sub 6/D/sub 6//D/sub 2/O at several temperatures The constants K/sup 0/ and K/sub 1/ are sensitive to temperature and to isotopic label. The vapor pressure results have been supplemented with measurements of the apparent molar volumes of the solutions listed above, as well as for H/sub 2/O/sup -/ and D/sub 2/O-rich solutions of toluene and deuteriotoluene,more » and with determinations of the solubilities and solubility isotope effects of the toluene solutions. The data have been interpreted in the context of the theory of isotope effects in condensed-phase systems. That analysis indicates that a significant dynamical vibrational coupling between solute and solvent normal modes occurs in these solutions. The result is of interest particularly as it pertains to models of the hydrophobic interaction.« less
  • We report an improved dynamic determination of the Casimir pressure P {sup expt} between two plane plates obtained using a micromachined torsional oscillator. The main improvements in the current experiment are a significant suppression of the surface roughness of the Au layers deposited on the interacting surfaces, and a decrease by a factor of 1.7 (down to 0.6 nm) in the experimental error in the measurement of the absolute separation. A metrological analysis of all data for P {sup expt} from 15 sets of measurements permitted us to determine both the random and systematic errors, and to find the totalmore » experimental error in P {sup expt} as a function of separation at the 95% confidence level. In contrast to all previous experiments on the Casimir effect, where a small relative error was achieved only at the shortest separation, our smallest experimental error ({approx}0.5%) is achieved over a wide separation range. The theoretical Casimir pressures P {sup theor} in the experimental configuration were calculated by the use of four theoretical approaches suggested in the literature based on the Lifshitz formula at nonzero temperature. All corrections to the Casimir force due to grain structure of the overlying metal layers (including the variation of optical data and patch potentials), surface roughness (including nonmultiplicative and diffraction-type effects), and nonlocal effects, were calculated or estimated. The maximum value of the roughness correction, achieved at the shortest separation of 160 nm, is equal to only 0.65% of the Casimir pressure. All theoretical errors, including those introduced by the proximity force theorem, finite size of the plate area, and uncertainties in the experimental separations, were analyzed and metrologically combined to obtain the total theoretical error at the 95% confidence level. Finally, the confidence interval for (P {sup theor} - P {sup expt}) was obtained as a function of separation. Our measurements are found to be consistent with two theoretical approaches utilizing the plasma model and the surface impedance over the entire measurement region from 160 to 750 nm. Two other approaches to the thermal Casimir force, utilizing the Drude model or a special prescription for the determination of the zero-frequency contribution to the Lifshitz formula, are excluded on the basis of our measurements at the 99 and 95% confidence levels, respectively. Finally, constraints on Yukawa-type hypothetical interactions are strengthened by up to a factor of 20 in a wide interaction range.« less