Electronic and nuclear quantum effects on the ice XI/ice Ih phase transition

Pamuk, Betül; Allen, Philip B.; Fernández-Serra, M.-V.

doi:10.1103/physrevb.92.134105

Cited by 22 publications

(29 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Some of the common force-fields for water wrongly predict a normal isotope effect, but DFT calculations generally give the observed anomalous isotope effect, at least with the XC functionals examined so far. It has been noted recently [241] that the same mechanism leads to an interesting isotope effect on the temperature of the transition from ice Ih to XI.…”

Section: Ice Structuresmentioning

confidence: 80%

Perspective: How good is DFT for water?

Gillan

Alfè

Michaelides

2016

The Journal of Chemical Physics

698

687

View full text Add to dashboard Cite

This article presents a perspective on Kohn-Sham density functional theory (KS-DFT) for electronic structure calculations in chemical physics. This theory is in widespread use for applications to both molecules and solids. We pay special attention to several aspects where there are both concerns and progress toward solutions. These include: 1. The treatment of open-shell and inherently multiconfig-urational systems (the latter are often called multireference systems and are variously classified as having strong correlation, near-degeneracy correlation, or high static correlation; KS-DFT must treat these systems with broken-symmetry determinants). 2. The treatment of noncovalent interactions. 3. The choice between developing new functionals by parametrization, by theoretical constraints, or by a combination. 4. The ingredients of the exchange-correlation functionals used by KS-DFT, including spin densities, the magnitudes of their gradients, spin-specific kinetic energy densities, nonlocal exchange (Hartree-Fock exchange), nonlocal correlation, and subshell-dependent corrections (DFT+U). 5. The quest for a universal functional, where we summarize some of the success of the latest Minnesota functionals, namely MN15-L and MN15, which were obtained by optimization against diverse databases. 6. Time-dependent density functional theory, which is an extension of DFT to treat time-dependent problems and excited states. The review is a snapshot of a rapidly moving field, and-like Marcel Duchamp-we hope to convey progress in a stimulating way. Published by AIP Publishing. [http://dx.

show abstract

Section: Ice Structuresmentioning

confidence: 80%

Perspective: How good is DFT for water?

Gillan

Alfè

Michaelides

2016

The Journal of Chemical Physics

698

687

View full text Add to dashboard Cite

show abstract

“…6 The presence or absence of ions has also been shown to control the occurrence of phase transitions and is linked to quantum effects in phases of water. 8,9 The structure of magnesium chloride hydrates, in particular the high-pressure hydrate MgClÁ2.10D 2 O at 2.5 gigapascal, also includes Mg 2+ in octahedral geometry 10 similar to what is observed for Li + . The difference in the behaviour of NaCl-solutions under compression raises the question of whether Na + ions can also be included in ice VII or not.…”

mentioning

confidence: 77%

Probing ice VII crystallization from amorphous NaCl–D₂O solutions at gigapascal pressures

Ludl

Bove

Corradini

et al. 2017

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…Our experimental results regarding the common 5 K shift model account for the results of previous studies on the NQEs on thermodynamic properties even though the exact value of the temperature shift varies between 4 and 7 K depending on the properties. For example, the melting temperature (3.82 K shift) and the temperature of density maximum (7.21 K shift) around ambient condition, singular temperature (5 K shift) in the deeply supercooled regime 075502-4 [13,14], and the phase transition between ice XI and ice Ih (4 K shift) at around 75 K [42] commonly correspond to ∼5 K shift. Temperature-dependent NQEs on thermodynamics, such as molar density and isothermal compressibility, are shown in Figs.…”

mentioning

confidence: 99%

Temperature-Independent Nuclear Quantum Effects on the Structure of Water

Kim¹,

Pathak²,

Späh³

et al. 2017

Phys. Rev. Lett.

View full text Add to dashboard Cite

Nuclear quantum effects (NQEs) have a significant influence on the hydrogen bonds in water and aqueous solutions and have thus been the topic of extensive studies. However, the microscopic origin and the corresponding temperature dependence of NQEs have been elusive and still remain the subject of ongoing discussion. Previous x-ray scattering investigations indicate that NQEs on the structure of water exhibit significant temperature dependence [Phys. Rev. Lett. 94, 047801 (2005)PRLTAO0031-900710.1103/PhysRevLett.94.047801]. Here, by performing wide-angle x-ray scattering of H_{2}O and D_{2}O droplets at temperatures from 275 K down to 240 K, we determine the temperature dependence of NQEs on the structure of water down to the deeply supercooled regime. The data reveal that the magnitude of NQEs on the structure of water is temperature independent, as the structure factor of D_{2}O is similar to H_{2}O if the temperature is shifted by a constant 5 K, valid from ambient conditions to the deeply supercooled regime. Analysis of the accelerated growth of tetrahedral structures in supercooled H_{2}O and D_{2}O also shows similar behavior with a clear 5 K shift. The results indicate a constant compensation between NQEs delocalizing the proton in the librational motion away from the bond and in the OH stretch vibrational modes along the bond. This is consistent with the fact that only the vibrational ground state is populated at ambient and supercooled conditions.

show abstract

Electronic and nuclear quantum effects on the ice XI/ice Ih phase transition

Cited by 22 publications

References 52 publications

Perspective: How good is DFT for water?

Perspective: How good is DFT for water?

Probing ice VII crystallization from amorphous NaCl–D₂O solutions at gigapascal pressures

Temperature-Independent Nuclear Quantum Effects on the Structure of Water

Contact Info

Product

Resources

About

Electronic and nuclear quantum effects on the ice XI/ice Ih phase transition

Cited by 22 publications

References 52 publications

Perspective: How good is DFT for water?

Perspective: How good is DFT for water?

Probing ice VII crystallization from amorphous NaCl–D2O solutions at gigapascal pressures

Temperature-Independent Nuclear Quantum Effects on the Structure of Water

Contact Info

Product

Resources

About

Probing ice VII crystallization from amorphous NaCl–D₂O solutions at gigapascal pressures