Pascal, Tod A. and Schärf, Daniel and Jung, Yousung and Kühne, Thomas D. (2012) On the absolute thermodynamics of water from computer simulations: A comparison of first-principles molecular dynamics, reactive and empirical force fields. Journal of Chemical Physics, 137 (24). Art. No. 244507 . ISSN 0021-9606 http://resolver.caltech.edu/CaltechAUTHORS:20130131-095211301
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We present the absolute enthalpy, entropy, heat capacity, and free energy of liquid water at ambient conditions calculated by the two-phase thermodynamic method applied to ab initio, reactive and classical molecular dynamics simulations. We find that the absolute entropy and heat capacity of liquid water from ab initio molecular dynamics (AIMD) is underestimated, but falls within the range of the flexible empirical as well as the reactive force fields. The origin of the low absolute entropy of liquid water from AIMD simulations is due to an underestimation of the translational entropy by 20% and the rotational entropy by 40% compared to the TIP3P classical water model, consistent with previous studies that reports low diffusivity and increased ordering of liquid water from AIMD simulations. Classical MD simulations with rigid water models tend to be in better agreement with experiment (in particular TIP3P yielding the best agreement), although the TIP4P-ice water model, the only empirical force field that reproduces the experimental melting temperature, has the lowest entropy, perhaps expectedly. This reiterates the limitations of existing empirical water models in simultaneously capturing the thermodynamics of solid and liquid phases. We find that the quantum corrections to heat capacity of water can be as large as 60%. Although certain water models are computed to yield good absolute free energies of water compared to experiments, they are often due to the fortuitous enthalpy-entropy cancellation, but not necessarily due to the correct descriptions of enthalpy and entropy separately.
|Additional Information:||© 2012 American Institute of Physics. Received 11 September 2012; accepted 29 November 2012; published online 28 December 2012. This work was partially supported by the World Class University program (R31-2008-000-10055-0) of Korea; Energy, Environment, Water, and Sustainability Initiative funding from KAIST. D.S. would like to thank the Max Planck Graduate Center. T.D.K. acknowledges financial support from the MAINZ Graduate School of Excellence and the IDEE project of the Carl Zeiss Foundation.|
|Subject Keywords:||ab initio calculations; enthalpy; entropy; free energy; molecular dynamics method; specific heat; water|
|Classification Code:||PACS: 65.20.-w; 61.20.Ja|
|Official Citation:||On the absolute thermodynamics of water from computer simulations: A comparison of first-principles molecular dynamics, reactive and empirical force fields Tod A. Pascal, Daniel Scharf, Yousung Jung, and Thomas D. Kuhne, J. Chem. Phys. 137, 244507 (2012), DOI:10.1063/1.4771974|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Jason Perez|
|Deposited On:||31 Jan 2013 21:48|
|Last Modified:||31 Jan 2013 21:48|
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