Quasi-harmonic approximation of thermodynamic properties of ice Ih, II, and III

Ramı́rez, Rafael; Neuerburg, N.; Fernández-Serra, M.-V.; Herrero, Carlos P.

doi:10.1063/1.4737862

Cited by 59 publications

(81 citation statements)

References 72 publications

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“…This provides a description with less than 5% error for E vib . For ices II and III, we used the mean Grüneisen associated with the computed DoS family (Ramírez et al, ).…”

Section: Methodsmentioning

confidence: 99%

Holistic Approach for Studying Planetary Hydrospheres: Gibbs Representation of Ices Thermodynamics, Elasticity, and the Water Phase Diagram to 2,300 MPa

et al. 2020

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Gibbs energy representations for ices II, III, V, and VI are reported. These were constructed using new measurements of volumes at high pressure over a range of low temperatures combined with calculated vibrational energies grounded in statistical physics. The collection of representations are released within the open source SeaFreeze program, together with the Gibbs representation already known for ice Ih and water. This program allows accurate determination of thermodynamics properties (phase boundaries, density, specific heat, bulk modulus, thermal expansivity, chemical potentials) and seismic wave velocities over the entire range of conditions encountered in hydrospheres in our solar system (130-500 K to 2,300 MPa). These comprehensive representations allow exploration of the rich spectrum of thermodynamic behavior in the H 2 O system. Although these results are broadly applicable in science and engineering, their use is particularly relevant to habitability analysis, interior modeling, and future geophysical sounding of water-rich planetary bodies of our solar system and beyond. Key Points:• New X-Ray diffraction measurements covering the entire range of ice II, III, V and VI using state of the art high pressure techniques • The first Gibbs energy equations of states for ice II, III, V and VI (and first equations of state for ice II, III and V) • New open-source code SeaFreeze allows to explore water and ices thermodynamic at all conditions found in solar system planetary hydrospheres Supporting Information:• Supporting Information S1

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“…This provides a description with less than 5% error for E vib . For ices II and III, we used the mean Grüneisen associated with the computed DoS family (Ramírez et al, ).…”

Section: Methodsmentioning

confidence: 99%

Holistic Approach for Studying Planetary Hydrospheres: Gibbs Representation of Ices Thermodynamics, Elasticity, and the Water Phase Diagram to 2,300 MPa

et al. 2020

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“…Higher volume derivatives, such as B(T ), in general may require higher volume derivatives of E 0 and ω k . As shown in our recent contributions 33,44 , the first derivative in eq. 2 is a good approximation for hexagonal ice.…”

Section: A Free Energy Within Quasi-harmonic Approximationmentioning

confidence: 99%

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

2015

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We study the isotope effect on the temperature of the proton order/disorder phase transition between ice XI and ice Ih, using the quasi-harmonic approximation combined with ab initio density functional theory calculations. We show that this method is accurate enough to obtain a phase transition temperature difference between light ice (H2O) and heavy ice (D2O) of 6 K as compared to the experimental value of 4 K. More importantly, we are able to explain the origin of the isotope effect on the much debated large temperature difference observed in the phase transition. The source of the difference is directly linked to the physics behind the anomalous isotope effect on the volume of hexagonal ice that was recently explained in [Phys. Rev. Lett. 108, 193003 (2012)]. These results indicate that the same physics might be behind the isotope effects in transition temperatures between other ice phases.

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“…For the quantum simulations, the Trotter number L was taken proportional to the inverse temperature (L ∝ 1/T ), so that L T = 6000 K, which turns out to roughly keep a constant precision in the PIMD results at different temperatures. 64,65,67 We have considered rectangular simulation cells with similar side length in the x and y directions of the (x, y) reference plane, and periodic boundary conditions were assumed. We checked that using isotropic changes of the cell dimensions in the N P T simulations yielded for the studied variables the same results as allowing flexible cells (independent changes of x and y axis length along with deformations of the rectangular shape).…”

Section: Methodsmentioning

confidence: 99%

Quantum effects in graphene monolayers: Path-integral simulations

Herrero

Ramı́rez

2016

The Journal of Chemical Physics

113

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Path-integral molecular dynamics (PIMD) simulations have been carried out to study the influence of quantum dynamics of carbon atoms on the properties of a single graphene layer. Finitetemperature properties were analyzed in the range from 12 to 2000 K, by using the LCBOPII effective potential. To assess the magnitude of quantum effects in structural and thermodynamic properties of graphene, classical molecular dynamics simulations have been also performed. Particular emphasis has been laid on the atomic vibrations along the out-of-plane direction. Even though quantum effects are present in these vibrational modes, we show that at any finite temperature classical-like motion dominates over quantum delocalization, provided that the system size is large enough. Vibrational modes display an appreciable anharmonicity, as derived from a comparison between kinetic and potential energy of the carbon atoms. Nuclear quantum effects are found to be appreciable in the interatomic distance and layer area at finite temperatures. The thermal expansion coefficient resulting from PIMD simulations vanishes in the zero-temperature limit, in agreement with the third law of thermodynamics.

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Quasi-harmonic approximation of thermodynamic properties of ice Ih, II, and III

Cited by 59 publications

References 72 publications

Holistic Approach for Studying Planetary Hydrospheres: Gibbs Representation of Ices Thermodynamics, Elasticity, and the Water Phase Diagram to 2,300 MPa

Holistic Approach for Studying Planetary Hydrospheres: Gibbs Representation of Ices Thermodynamics, Elasticity, and the Water Phase Diagram to 2,300 MPa

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

Quantum effects in graphene monolayers: Path-integral simulations

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