DOI: 10.1063/1.2841127. A computational investigation of thermodynamics, structure, dynamics and solvation behavior in modified water models

A computational investigation of thermodynamics, structure, dynamics and solvation behavior in modified water models

10.1063/1.2841127

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

We investigate the properties of geometrically modified water models by performing molecular dynamics simulations of perturbations of the extended simple point charge (SPC/E) model of water over a wide range of temperatures at 1bar. The geometric modification consists of altering the H–O–H angle in SPC/E. The dipole moment is held constant by altering the O–H bond length, while the electrostatic charges are left unchanged. We find that a H–O–H angle of at least 100° is necessary for the appearance of density anomalies and of solubility extrema with respect to temperature for small apolar solutes. We observe the occurrence of two incompatible types of structural order in these models: Tetrahedral, with waterlike translational order for bent models with H–O–H angles in excess of 100°; and linear, with Lennard–Jones–like orientationally averaged translational order for smaller H–O–H angles. Increasing the H–O–H angle causes the density to increase, while at the same time shifting waterlike anomalies to progressively higher temperatures. For bent models with H–O–H angle greater than SPC/E’s, we observe arrest of translational motion at 300K (115°) and 330K (120°).

Bibliography

Chatterjee, S., Debenedetti, P. G., Stillinger, F. H., & Lynden-Bell, R. M. (2008). A computational investigation of thermodynamics, structure, dynamics and solvation behavior in modified water models. The Journal of Chemical Physics, 128(12).

Authors 4

Swaroop Chatterjee (first)
Pablo G. Debenedetti (additional)
Frank H. Stillinger (additional)
Ruth M. Lynden-Bell (additional)

References 33 Referenced 157

10.1088/0953-8984/15/45/R01 / J. Phys.: Condens. Matter (2003)
10.1080/00268970110041632 / Mol. Phys. (2001)
10.1021/jp0458553 / J. Phys. Chem. B (2005)
10.1080/00268970601022727 / Mol. Phys. (2006)
10.1021/jp068581n / J. Phys. Chem. B (2007)
10.1021/j100308a038 / J. Phys. Chem. (1987)
10.1016/0009-2614(93)89362-L / Chem. Phys. Lett. (1993)
10.1063/1.465158 / J. Chem. Phys. (1993)
10.1103/PhysRevLett.88.225503 / Phys. Rev. Lett. (2002)
10.1063/1.481505 / J. Chem. Phys. (2000)
10.1021/jp074418w / J. Phys. Chem. C (2007)
10.1039/b703873a / Phys. Chem. Chem. Phys. (2007)
10.1063/1.448118 / J. Chem. Phys. (1984)
{'volume-title': 'Computer Simulation of Liquids', 'year': '1987', 'key': '2023062001185661300_c14'} / Computer Simulation of Liquids (1987)
10.1016/0021-9991(77)90098-5 / J. Comput. Phys. (1977)
10.1063/1.1734110 / J. Chem. Phys. (1963)
10.1103/PhysRevA.25.978 / Phys. Rev. A (1982)
10.1103/PhysRevE.71.061505 / Phys. Rev. E (2005)
{'edition': '3rd ed.', 'volume-title': 'Mechanics', 'year': '1976', 'key': '2023062001185661300_c19'} / Mechanics (1976)
10.1103/PhysRevLett.84.2064 / Phys. Rev. Lett. (2000)
10.1103/PhysRevE.62.993 / Phys. Rev. E (2000)
10.1063/1.1532344 / J. Chem. Phys. (2003)
10.1038/35053024 / Nature (London) (2001)
10.1080/002689798169195 / Mol. Phys. (1998)
10.1063/1.467949 / J. Chem. Phys. (1994)
10.1063/1.472313 / J. Chem. Phys. (1996)
10.1016/S0009-2614(03)01044-3 / Chem. Phys. Lett. (2003)
10.1063/1.2056539 / J. Chem. Phys. (2005)
10.1063/1.1676585 / J. Chem. Phys. (1971)
10.1103/PhysRevLett.84.2064 / Phys. Rev. Lett. (2000)
10.1103/PhysRevE.66.011202 / Phys. Rev. E (2002)
10.1103/PhysRevLett.95.130604 / Phys. Rev. Lett. (2005)
10.1063/1.1436479 / J. Chem. Phys. (2002)

Dates

Type	When
Created	17 years, 4 months ago (March 27, 2008, 6:33 p.m.)
Deposited	2 years, 2 months ago (June 19, 2023, 9:19 p.m.)
Indexed	1 week, 2 days ago (Aug. 12, 2025, 5:36 p.m.)
Issued	17 years, 4 months ago (March 27, 2008)
Published	17 years, 4 months ago (March 27, 2008)
Published Online	17 years, 4 months ago (March 27, 2008)
Published Print	17 years, 4 months ago (March 28, 2008)

Funders 0

None

BibTeX

@article{Chatterjee_2008, title={A computational investigation of thermodynamics, structure, dynamics and solvation behavior in modified water models}, volume={128}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.2841127}, DOI={10.1063/1.2841127}, number={12}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Chatterjee, Swaroop and Debenedetti, Pablo G. and Stillinger, Frank H. and Lynden-Bell, Ruth M.}, year={2008}, month=mar }

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