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Quantum path integral simulation of isotope effects in the melting temperature of ice Ih
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10.1063/1.3503764
/content/aip/journal/jcp/133/14/10.1063/1.3503764
http://aip.metastore.ingenta.com/content/aip/journal/jcp/133/14/10.1063/1.3503764

Figures

Image of FIG. 1.
FIG. 1.

OO RDFs derived from quantum and classical simulations of water at 298 K and density of . For comparison, the PI MD results of Ref. 12 are shown as open circles.

Image of FIG. 2.
FIG. 2.

OH RDFs derived from quantum and classical simulations of water at 298 K and density of . For comparison, the PI MD results of Ref. 12 are shown as open circles.

Image of FIG. 3.
FIG. 3.

HH RDFs derived from quantum and classical simulations of water at 298 K and density of . For comparison, the PI MD results of Ref. 12 are shown as open circles.

Image of FIG. 4.
FIG. 4.

Density of water at 1 atm pressure obtained from classical and PI MD simulations. Lines are cubic polynomial fits to the simulation data.

Image of FIG. 5.
FIG. 5.

The relative free energy of liquid water as a function of the hydrogen isotope mass. The open circles correspond to the masses of H, D, and T, respectively. The result was obtained by nonequilibrium simulations with the AS method at the reference state point .

Image of FIG. 6.
FIG. 6.

The relative free energy of normal water and ice at pressure of 1 atm as determined by our RS simulations. The melting point is .

Image of FIG. 7.
FIG. 7.

The relative free energy of deuterated water and ice at pressure of 1 atm as determined by our RS simulations. The melting point is .

Image of FIG. 8.
FIG. 8.

The relative free energy of tritiated water and ice at pressure of 1 atm as determined by our RS simulations. The melting point is .

Image of FIG. 9.
FIG. 9.

The function obtained for liquid water by nonequilibrium AS simulations at the reference state point . The extrapolation is shown for the solid and liquid phases in the inset of the figure.

Image of FIG. 10.
FIG. 10.

The relative free energy of water and ice at pressure of 1 atm as determined by our RS simulations in the classical limit. The melting point is .

Image of FIG. 11.
FIG. 11.

Gibbs free energy difference between ice and water as a function of the molecular mass at the reference state point . Depending on the molecular mass, the KE of the liquid may be larger than that of the solid .

Image of FIG. 12.
FIG. 12.

Kinetic energy difference between ice and water as a function of the molecular mass at the reference state point . The line is a guide to the eye.

Image of FIG. 13.
FIG. 13.

Intramolecular OH distance of ice and water as a function of the molecular mass at the reference state point . Lines are guides to the eye. The inset shows the quasiharmonic stretch frequency (in ) as a function of the OH distance for the q-TIP4P/F potential. was derived from the second derivative of the potential energy with respect the OH bond distance and by considering the actual O and H masses.

Tables

Generic image for table
Table I.

Molecular properties (bond distance, bond angle, and dipole moment) as well as kinetic and potential energy of liquid water at 298 K and density . is the distance of the RDF maximum associated with the H bond. The KE is partitioned into H-isotope and O-atom contributions ( and , respectively). is the maximum density of water at TMD, as derived from simulations at . Both classical and quantum results are given. The quantum results correspond to normal , heavy , and tritiated water.

Generic image for table
Table II.

Relative free energies of tritiated water at the reference point as derived by independent AS simulations of different lengths. For a given simulation length, two results are presented, corresponding to simulations where the initial and final integration limits are interchanged. The last column shows the average of both independent runs.

Generic image for table
Table III.

Relative free energy at the reference point (, ) of solid and liquid phases of normal, heavy, and tritiated water. is given in , and its estimated error is . The last column summarizes the results obtained in the classical limit .

Generic image for table
Table IV.

Computational conditions used in the nonequilibrium RS simulations to determine the temperature dependence of the relative Gibbs free energy of the studied isotope compositions of water and ice.

Generic image for table
Table V.

Melting temperature, entropy, and enthalpy for normal, heavy, and tritiated water as well as classical limit results at ambient pressure. The melting enthalpy was estimated by two independent methods. The change in the kinetic and potential energies upon melting (liquid minus solid values) and the molar volume of the solid and liquid phases are also given. The standard error in the final digits is given in parenthesis.

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/content/aip/journal/jcp/133/14/10.1063/1.3503764
2010-10-13
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Quantum path integral simulation of isotope effects in the melting temperature of ice Ih
http://aip.metastore.ingenta.com/content/aip/journal/jcp/133/14/10.1063/1.3503764
10.1063/1.3503764
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