Nuclear Quantum Effects in Water

Morrone, Joseph A.; Car, Roberto

doi:10.1103/physrevlett.101.017801

Cited by 411 publications

(588 citation statements)

References 44 publications

Supporting

Mentioning

523

Contrasting

Unclassified

Order By: Relevance

“…Two main differences between our simulation and the experiments are a shift of the second peak in the O-O curve to shorter distances and more structured long-range regions predicted by our potential. For better comparison we should carry out quantum mechanical simulations rather than classical simulations since a significant softening of the structure may occur [88,89,90]. Indeed, in a recent series of path-integral simulations [90] it was found that the first peak of the O-O g(r) was lowered by about 0.4 compared to classical dynamics simulation, which corresponds closely with the discrepancy in peak height observed here in Figure 12.…”

Section: Liquid Watersupporting

confidence: 75%

A transferable H2O interaction potential based on a single center multipole expansion: SCME

Wikfeldt

Batista

Vila

et al. 2013

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Abstract. A transferable potential energy function for describing the interaction between water molecules is presented. The electrostatic interaction is described rigorously using a multipole expansion. Only one expansion center is used per molecule to avoid the introduction of monopoles. This single center approach turns out to converge and give close agreement with ab initio calculations when carried out up to and including the hexadecapole. Both dipole and quadrupole polarizability is included. All parameters in the electrostatic interaction as well as the dispersion interaction are taken from ab initio calculations or experimental measurements of a single water molecule. The repulsive part of the interaction is parametrized to fit ab initio calculations of small water clusters and experimental measurements of ice I h . The parametrized potential function was then used to simulate liquid water and the results agree well with experiment, even better than simulations using some of the point charge potentials fitted to liquid water. The evaluation of the new interaction potential for condensed phases is fast because point charges are not present and the interaction can, to a good approximation, be truncated at a finite range.

show abstract

Section: Liquid Watersupporting

confidence: 75%

A transferable H2O interaction potential based on a single center multipole expansion: SCME

Wikfeldt

Batista

Vila

et al. 2013

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…Moreover, it is known from classical 7 and DFT based simulations that, for flexible water models, the inclusion of nuclear quantum effects leads to less structured liquid and improve the density behavior. [67][68][69][70] By observing that these effects are less pronounced in D 2 O than in H 2 O and that the former has a molar density 1.3% higher than the latter, we expect the inclusion of this correction to reduce further the density. 69,71 This result stands also in sharp contrast to that of BLYP, a dispersion free functional that yields 0.797 g/mL.…”

mentioning

confidence: 99%

“…This difference is in part explained by the fact that our simulations ignore nuclear quantum effects, which influence this property. [67][68][69][70] The coordination number, which condenses the 10 second peak with inclusion of dispersion has been discussed by Møgelhøj et al in Ref. 25 .…”

mentioning

confidence: 99%

Bulk Liquid Water at Ambient Temperature and Pressure from MP2 Theory

Ben

Schönherr

Hutter

et al. 2013

J. Phys. Chem. Lett.

137

112

View full text Add to dashboard Cite

MP2 provides a good description of hydrogen bonding in water clusters and includes longrange dispersion interactions without the need to introduce empirical elements in the description of the interatomic potential. To assess its performance for bulk liquid water under ambient conditions, an isobaric-isothermal (NpT) Monte Carlo simulation at the second-order Moller-Plesset perturbation theory level (MP2) has been performed. The obtained value of the water density is excellent (1.02 g/mL), and the calculated radial distribution functions are in fair agreement with experimental data. The MP2 results are compared to a few density functional approximations, including semilocal functionals, hybrid functionals, and functionals including empirical dispersion corrections. These results demonstrate the feasibility of directly sampling the potential energy surface of condensed-phase systems using correlated wave function theory, and their quality paves the way for further applications. Understanding the structural and electronic properties of liquid water at ambient conditions is a major challenge in condensed matter simulations. Water is a crucial ingredient for a large variety of systems of prime importance in basic chemistry, biology, and physics, as well as in the applied fields of catalysis and energy production. The water molecule has a large dipole moment and polarizability, is a multiple hydrogen donor and acceptor and can easily build network structures.The total cohesive energy in the condensed phase is, as a consequence of these properties, a sum of many weak interactions. Theoretical models face therefore the challenge to describe many different effects and their subtle interplay at a high precision. The development of sophisticated empirical potentials for water 1-10 , allowed to gain insights into water's behavior and its thermodynamic properties [11][12][13] , such as, density maxima, heat capacity and effects of supercooling. However, empirical models lack transferability and might fail if used under conditions away from their fitting range. Most importantly, as soon as water takes an active role in a chemical process, either as a strongly interacting solvent, or for example as a source of protons, the electronic properties of the water molecule need to be taken into account. In this respect, first-principles methods offer the possibility to describe all the underlying physics on the same footing, simplifying the treatment of intra-and inter-molecular interactions. The capability to reproduce properties of complex systems such as liquid water can therefore be used to judge the sophistication and predictive power of a given quantum mechanical model. Density functional theory (DFT) is the most used quantum mechanical method employed for studying physical and chemical properties of condensed phase systems. Many DFT based simulation of bulk water have been reported in the literature, and in this context three main methods of sampling the phase space can be recognized 14 : the Car-Parrinello molecula...

show abstract

“…In the case of water protons for instance, n(p) provides a richness of information about the potential surface that the proton experiences, including the effects of hydrogen bonding. DINS complements microscopic structural studies and allows a quantitative comparison with quantum Monte Carlo simulations [8,9]. These possibilities and a variety of successful experiments on light atoms and molecules make DINS technique a unique and well established tool to investigate the hydrogen bonding [17] and intermolecular structure of water under various conditions [11].…”

mentioning

confidence: 99%

“…For example, differences in n(p) between liquid water and ice re ect the breaking and distortion of hydrogen bonds that occurs upon melting [6,9].…”

mentioning

confidence: 99%

Quantum effects in water: proton kinetic energy maxima in stable and supercooled liquid

Pietropaolo¹,

Senesi²,

Mayers³

2009

Braz. J. Phys.

View full text Add to dashboard Cite

A strong temperature dependence of proton mean kinetic energy was observed for liquid water around the density maximum and for moderately supercooled water. Line shape analysis of proton momentum distribution, determined from deep inelastic neutron scattering measurements, shows that there are two proton kinetic energy maxima, one at the same temperature of the macroscopic density maximum at 277 K, and another one in the supercooled phase located around 270 K. The maximum at 277 K is a microscopic quantum counterpart of the macroscopic density maximum, where energetic balance giving rise to the local water structure is manifest in the temperature dependence of kinetic energy. The maximum in the supercooled phase, with higher kinetic energy with respect to stable phases, is associated to changes in the proton potential as the structure evolves with a large number of H-bond units providing both stronger effective proton localization, as well as proton quantum delocalization.

show abstract

Nuclear Quantum Effects in Water

Cited by 411 publications

References 44 publications

A transferable H2O interaction potential based on a single center multipole expansion: SCME

A transferable H2O interaction potential based on a single center multipole expansion: SCME

Bulk Liquid Water at Ambient Temperature and Pressure from MP2 Theory

Quantum effects in water: proton kinetic energy maxima in stable and supercooled liquid

Contact Info

Product

Resources

About