title: Nuclear Quantum Effects in Water and Aqueous Systems: Experiment, Theory, and Current Challenges.
abstract: 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 principle of competing quantum effects that allows the subtle interplay of water's quantum effects and their manifestation in experimental observables to 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 this area of research.
authors.affiliation: Laboratory of Computational Science and Modeling, Institute of Materials, École Polytechnique Fédérale de Lausanne , 1015 Lausanne, Switzerland.
authors.forename: Michele
authors.initials: M
authors.lastname: Ceriotti
authors.affiliation: Thomas Young Centre, London Centre for Nanotechnology and Department of Physics and Astronomy, University College London , London WC1E 6BT, United Kingdom.
authors.forename: Wei
authors.initials: W
authors.lastname: Fang
authors.affiliation: Department of Chemistry, University of Calgary , 2500 University Drive NW, Calgary, Alberta T2N 1N4, Canada.
authors.forename: Peter G
authors.initials: PG
authors.lastname: Kusalik
authors.affiliation: School of Mathematics and Physics, University of Queensland , Brisbane, 4072 Queensland Australia.
authors.forename: Ross H
authors.initials: RH
authors.lastname: McKenzie
authors.affiliation: Thomas Young Centre, London Centre for Nanotechnology and Department of Physics and Astronomy, University College London , London WC1E 6BT, United Kingdom.
authors.forename: Angelos
authors.initials: A
authors.lastname: Michaelides
authors.affiliation: Lawrence Livermore National Laboratory , Livermore, California 94550, United States.
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Morales
authors.affiliation: Department of Chemistry, Stanford University , 333 Campus Drive, Stanford, California 94305, United States.
authors.forename: Thomas E
authors.initials: TE
authors.lastname: Markland