A.G.Kalinichev: Aqueous Solutions at Interfaces and in Nanopores

Monte Carlo (MC) and molecular dynamics (MD) computer simulations

Aqueous mixtures in the system H₂O-CO₂-NaCl

is a good approximation for most fluids naturally occurring in the Earth’s crust and mantle. Although there are many experimental thermodynamic data for this system and several empirical equations of state there have been suggested for geologically relevant temperatures and pressures, adequate molecular-level understanding of their properties is still lacking. Despite significant recent progress in molecular computer simulations of water aqueous solutions over wide ranges of thermodynamic conditions, fluid CO₂ and H₂O-CO₂ mixtures have been simulated in much less detail.

Our objective is to systematically investigate by MD computer simulations thermodynamic, structural, transport, and spectroscopic properties of fluids in the system H₂O-CO₂-NaCl at geochemically relevant temperatures, pressures, and concentrations.

Research papers

P.Kumar, A.G.Kalinichev, R.J.Kirkpatrick (2007) Dissociation of carbonic acid: Gas phase energetics and mechanism from ab initio metadynamics simulations. J.Chem.Phys., 126, 204315-1-7.   [pdf 393kB]

I.S.Ufimtsev, A.G.Kalinichev, T.J.Martinez, R.J.Kirkpatrick (2007) A charged ring model for classical OH^-(aq) simulations. Chem.Phys.Lett., 442, 128-133.   [pdf 533kB]

G.V.Bondarenko, Yu.E.Gorbaty, A.V.Okhulkov, A.G.Kalinichev (2006) Structure and hydrogen bonding in liquid and supercritical aqueous NaCl solutions at a pressure of 1000 bar and temperatures up to 500^oC: A comprehensive experimental and computational study. J.Phys.Chem.A, 110, 4042-4052.   [pdf 274kB]

N.I.Bezmen, V.A.Zharikov, V.O.Zevel’sky, A.G.Kalinichev (2005) Melting of alkali aluminosilicate systems under hydrogen–water fluid pressure, P_tot = 2 kbar. Petrology, 13, 407-426.   [pdf 296kB]

G.V.Bondarenko, Yu.E.Gorbaty, A.G.Kalinichev, A.V.Okhulkov (2004) Complex study of liquid and supercritical aqueous solutions of electrolytes by methods of vibrational spectroscopy, x-ray diffraction, and molecular dynamics. In: Experimental Mineralogy: Some Results at the Turn of the Century, V.A.Zharikov, ed. Moscow, Nauka Publishing, v.2, pp.15-25 (in Russian).

G.V.Bondarenko, Yu.E.Gorbaty, A.G.Kalinichev, A.V.Okhulkov, V.K.Popov (2002) A comprehensive study of NaCl aqueous solution at a constant pressure of 1000 bar in the temperature range 20–500^oC. Chemical Engineering Transactions, 2(1), 79-85.

A.G.Kalinichev (2001) Molecular simulations of liquid and supercritical water: Thermodynamics, structure, and hydrogen bonding. Reviews in Mineralogy and Geochemistry, 42, 83-129.   [pdf 775 kB]

A.G.Kalinichev, S.V.Churakov (2001) Thermodynamics and structure of molecular clusters in supercritical water. Fluid Phase Equilibria, 183, 271-278.   [pdf 119KB]

A.G.Kalinichev, Yu.E.Gorbaty, G.V.Bondarenko, A.V.Okhulkov (2000) The effect of pressure on hydrogen bonding in water. In: Steam, Water, and Hydrothermal Systems. Physics and Chemistry Meeting the Needs of Industry. NRC-CNRC, Ottawa, Canada, p.538-545.

A.G.Kalinichev, Yu.E.Gorbaty, A.V.Okhulkov (1999) Structure and hydrogen bonding of liquid water at high hydrostatic pressures: Monte Carlo NPT-ensemble simulation up to 10 kbar. J.Mol.Liquids., 82, 57-7.   [pdf 739KB]

A.G.Kalinichev, S.V.Churakov (1999) Size and topology of molecular clusters in supercritical water: A molecular dynamics simulation. Chem.Phys.Lett., 302, 411-417.   [pdf 168KB]

Yu.E.Gorbaty, G.V.Bondarenko, A.G.Kalinichev, A.V.Okhulkov (1999) The effect of pressure on hydrogen bonding in water: IR study of n_OD HDO at pressures of up to 1500 bar. Mol.Phys., 96, 1659-1665.   [pdf 215KB]

A.G.Kalinichev, Yu.E.Gorbaty (1998) The role of hydrogen bonding in the structure and properties of hydrothermal fluids. In: Experimental and Theoretical Modeling of Mineral Formation Processes. Moscow, Nauka Publishing, pp.242-264 (in Russian).

A.G.Kalinichev, J.D.Bass (1997) Hydrogen bonding in supercritical water. 2. Computer simulations. J.Phys.Chem.A, 101, 9720-9727.   [pdf 253KB]

Yu.E.Gorbaty, A.G.Kalinichev (1995) Hydrogen bonding in supercritical water. 1. Experimental results. J.Phys.Chem., 99, 5336-5340.   [pdf 622kB]

A.G.Kalinichev, K.Heinzinger (1995) Molecular dynamics of supercritical water: A computer simulation of vibrational spectra with the flexible BJH potential. Geochimica et Cosmochimica Acta, 59, 641-650.   [pdf 794KB]

A.G.Kalinichev, J.D.Bass (1995) Computer simulations of supercritical water over a wide range of densities. In: Physical Chemistry of Aqueous Systems. Meeting the Needs of Industry. Ed. by H.J.White Jr., J.V.Sengers, D.B.Neumann, J.C.Bellows. Begell House, New York, 245-252.

A.G.Kalinichev, J.D.Bass (1994) Hydrogen bonding in supercritical water: a Monte Carlo simulation. Chem.Phys.Lett., 231, 301-307.   [pdf 661KB]

A.G.Kalinichev (1993) Molecular dynamics and self-diffusion in supercritical water. Ber.Bunsenges.Phys.Chem., 97, 872-876.

A.G.Kalinichev, K.Heinzinger (1992) Computer Simulations of Aqueous Fluids at High Temperatures and Pressures. In: Thermodynamic Data: Systematics and Estimation, ed. by S.K.Saxena. Advances in Physical Geochemistry, 10,1-59.

A.G.Kalinichev (1992) Monte Carlo simulations of water under supercritical conditions. II. Convergence characteristics and the system size effects. Z.Naturforsch., 47a, 992-998.

A.G.Kalinichev (1991) Monte Carlo simulations of water under supercritical conditions. I.Thermodynamic and structural properties. Z.Naturforsch., 46a, 433-444.

Z.Slanina, A.G.Kalinichev (1991) A configurational contribution to the heat capacity of gaseous (HDO)2. Z.Naturforsch., 46a, 39-42.

A.G.Kalinichev (1991) Theoretical modeling of geochemical fluids under high-pressure, high-temperature conditions. High Pressure Research, 7, 378-380.

A.G.Kalinichev (1986) Monte Carlo study of the thermodynamics and structure of dense supercritical water. Intern.J.Thermophys., 7, 887-900.   [pdf 456kB]

A.G.Kalinichev (1985) A Monte Carlo study of dense supercritical water. High Temperature, 23, 544-548.

Invited Talks and Seminars

A.G.Kalinichev, T.V.Gerya (2005) Phase separation of metamorphic fluids: Molecular dynamics modeling of a generalized system H2O-CO2-NaCl at high temperatures and pressures. International School of Earth's Sciences, Odessa, Ukraine, August 2005.

A.G.Kalinichev (2004) Classical Monte Carlo and molecular dynamics computer simulations. American Chemical Society and Petroleum Research Fund Summer School "Molecular Modeling Applied to Environmental Geochemistry", University Park, PA, August 2004.

A.G.Kalinichev (2004) Molecular Computer Simulations of Aqueous Solutions and Mineral-Solution Interfaces. Department of Physics, University of California Berkeley, Berkeley, CA, February 26, 2004.

A.G.Kalinichev, T.V.Gerya (2003) Phase separation of metamorphic fluid upon cooling: Molecular dynamics simulation of a generalized H2O-CO2-NaCl system at high temperatures and pressures. Symposium "Magmatism, Metamorphism, and Geodynamics", Chernogolovka, Russia, November 22, 2003.

A.G.Kalinichev (2003) Molecular simulations of liquid and supercritical water: thermodynamics, structure,and hydrogen bonding. Laboratory of Mathematical and Physical Modeling in Hydrodynamics, Institute for Problems in Mechanics, Russian Academy of Sciences, Moscow, Russia, May 30, 2003.

A.G.Kalinichev (2001) Molecular simulations of liquid and supercritical water: Thermodynamics, structure, and hydrogen bonding. Mineralogical Society of America - Geochemical Society Short Course “Molecular Modeling Theory: and Applications in the Geosciences”, Roanoke, VA, May 2001.

A.G.Kalinichev (1998) Hydrogen bond dynamics in supercritical water. VIIth International Conference "Problems of solvation and complex formation in solutions", Ivanovo, Russia, p.462.

A.G.Kalinichev (1997) Supercritical water as a medium for a new generation of environmentally friendly and energy efficient technologies of the XXI century (opening lecture). Moscow Seminar on Supercritical Fluids Science and Technology, Moscow, November 1997.

A.G.Kalinichev (1996) Structute and Hydrogen Bonding in Liquid and Supercritical Water: Experimental Studies and Computer Simulations EMLG Annual Meeting "Structure and Thermodynamics of Solvents and Solutions". Balatonfured, Hungary, September 1996.

Last updated: October 28, 2007

	Research papers
	P.Kumar, A.G.Kalinichev, R.J.Kirkpatrick (2007) Dissociation of carbonic acid: Gas phase energetics and mechanism from ab initio metadynamics simulations. J.Chem.Phys., 126, 204315-1-7. [pdf 393kB]
	I.S.Ufimtsev, A.G.Kalinichev, T.J.Martinez, R.J.Kirkpatrick (2007) A charged ring model for classical OH^-(aq) simulations. Chem.Phys.Lett., 442, 128-133. [pdf 533kB]
	G.V.Bondarenko, Yu.E.Gorbaty, A.V.Okhulkov, A.G.Kalinichev (2006) Structure and hydrogen bonding in liquid and supercritical aqueous NaCl solutions at a pressure of 1000 bar and temperatures up to 500^oC: A comprehensive experimental and computational study. J.Phys.Chem.A, 110, 4042-4052. [pdf 274kB]
	N.I.Bezmen, V.A.Zharikov, V.O.Zevel’sky, A.G.Kalinichev (2005) Melting of alkali aluminosilicate systems under hydrogen–water fluid pressure, P_tot = 2 kbar. Petrology, 13, 407-426. [pdf 296kB]
	G.V.Bondarenko, Yu.E.Gorbaty, A.G.Kalinichev, A.V.Okhulkov (2004) Complex study of liquid and supercritical aqueous solutions of electrolytes by methods of vibrational spectroscopy, x-ray diffraction, and molecular dynamics. In: Experimental Mineralogy: Some Results at the Turn of the Century, V.A.Zharikov, ed. Moscow, Nauka Publishing, v.2, pp.15-25 (in Russian).
	G.V.Bondarenko, Yu.E.Gorbaty, A.G.Kalinichev, A.V.Okhulkov, V.K.Popov (2002) A comprehensive study of NaCl aqueous solution at a constant pressure of 1000 bar in the temperature range 20–500^oC. Chemical Engineering Transactions, 2(1), 79-85.
	A.G.Kalinichev (2001) Molecular simulations of liquid and supercritical water: Thermodynamics, structure, and hydrogen bonding. Reviews in Mineralogy and Geochemistry, 42, 83-129. [pdf 775 kB]
	A.G.Kalinichev, S.V.Churakov (2001) Thermodynamics and structure of molecular clusters in supercritical water. Fluid Phase Equilibria, 183, 271-278. [pdf 119KB]
	A.G.Kalinichev, Yu.E.Gorbaty, G.V.Bondarenko, A.V.Okhulkov (2000) The effect of pressure on hydrogen bonding in water. In: Steam, Water, and Hydrothermal Systems. Physics and Chemistry Meeting the Needs of Industry. NRC-CNRC, Ottawa, Canada, p.538-545.
	A.G.Kalinichev, Yu.E.Gorbaty, A.V.Okhulkov (1999) Structure and hydrogen bonding of liquid water at high hydrostatic pressures: Monte Carlo NPT-ensemble simulation up to 10 kbar. J.Mol.Liquids., 82, 57-7. [pdf 739KB]
	A.G.Kalinichev, S.V.Churakov (1999) Size and topology of molecular clusters in supercritical water: A molecular dynamics simulation. Chem.Phys.Lett., 302, 411-417. [pdf 168KB]
	Yu.E.Gorbaty, G.V.Bondarenko, A.G.Kalinichev, A.V.Okhulkov (1999) The effect of pressure on hydrogen bonding in water: IR study of n_OD HDO at pressures of up to 1500 bar. Mol.Phys., 96, 1659-1665. [pdf 215KB]
	A.G.Kalinichev, Yu.E.Gorbaty (1998) The role of hydrogen bonding in the structure and properties of hydrothermal fluids. In: Experimental and Theoretical Modeling of Mineral Formation Processes. Moscow, Nauka Publishing, pp.242-264 (in Russian).
	A.G.Kalinichev, J.D.Bass (1997) Hydrogen bonding in supercritical water. 2. Computer simulations. J.Phys.Chem.A, 101, 9720-9727. [pdf 253KB]
	Yu.E.Gorbaty, A.G.Kalinichev (1995) Hydrogen bonding in supercritical water. 1. Experimental results. J.Phys.Chem., 99, 5336-5340. [pdf 622kB]
	A.G.Kalinichev, K.Heinzinger (1995) Molecular dynamics of supercritical water: A computer simulation of vibrational spectra with the flexible BJH potential. Geochimica et Cosmochimica Acta, 59, 641-650. [pdf 794KB]
	A.G.Kalinichev, J.D.Bass (1995) Computer simulations of supercritical water over a wide range of densities. In: Physical Chemistry of Aqueous Systems. Meeting the Needs of Industry. Ed. by H.J.White Jr., J.V.Sengers, D.B.Neumann, J.C.Bellows. Begell House, New York, 245-252.
	A.G.Kalinichev, J.D.Bass (1994) Hydrogen bonding in supercritical water: a Monte Carlo simulation. Chem.Phys.Lett., 231, 301-307. [pdf 661KB]
	A.G.Kalinichev (1993) Molecular dynamics and self-diffusion in supercritical water. Ber.Bunsenges.Phys.Chem., 97, 872-876.
	A.G.Kalinichev, K.Heinzinger (1992) Computer Simulations of Aqueous Fluids at High Temperatures and Pressures. In: Thermodynamic Data: Systematics and Estimation, ed. by S.K.Saxena. Advances in Physical Geochemistry, 10,1-59.
	A.G.Kalinichev (1992) Monte Carlo simulations of water under supercritical conditions. II. Convergence characteristics and the system size effects. Z.Naturforsch., 47a, 992-998.
	A.G.Kalinichev (1991) Monte Carlo simulations of water under supercritical conditions. I.Thermodynamic and structural properties. Z.Naturforsch., 46a, 433-444.
	Z.Slanina, A.G.Kalinichev (1991) A configurational contribution to the heat capacity of gaseous (HDO)2. Z.Naturforsch., 46a, 39-42.
	A.G.Kalinichev (1991) Theoretical modeling of geochemical fluids under high-pressure, high-temperature conditions. High Pressure Research, 7, 378-380.
	A.G.Kalinichev (1986) Monte Carlo study of the thermodynamics and structure of dense supercritical water. Intern.J.Thermophys., 7, 887-900. [pdf 456kB]
	A.G.Kalinichev (1985) A Monte Carlo study of dense supercritical water. High Temperature, 23, 544-548.

	Invited Talks and Seminars
	A.G.Kalinichev, T.V.Gerya (2005) Phase separation of metamorphic fluids: Molecular dynamics modeling of a generalized system H2O-CO2-NaCl at high temperatures and pressures. International School of Earth's Sciences, Odessa, Ukraine, August 2005.
	A.G.Kalinichev (2004) Classical Monte Carlo and molecular dynamics computer simulations. American Chemical Society and Petroleum Research Fund Summer School "Molecular Modeling Applied to Environmental Geochemistry", University Park, PA, August 2004.
	A.G.Kalinichev (2004) Molecular Computer Simulations of Aqueous Solutions and Mineral-Solution Interfaces. Department of Physics, University of California Berkeley, Berkeley, CA, February 26, 2004.
	A.G.Kalinichev, T.V.Gerya (2003) Phase separation of metamorphic fluid upon cooling: Molecular dynamics simulation of a generalized H2O-CO2-NaCl system at high temperatures and pressures. Symposium "Magmatism, Metamorphism, and Geodynamics", Chernogolovka, Russia, November 22, 2003.
	A.G.Kalinichev (2003) Molecular simulations of liquid and supercritical water: thermodynamics, structure,and hydrogen bonding. Laboratory of Mathematical and Physical Modeling in Hydrodynamics, Institute for Problems in Mechanics, Russian Academy of Sciences, Moscow, Russia, May 30, 2003.
	A.G.Kalinichev (2001) Molecular simulations of liquid and supercritical water: Thermodynamics, structure, and hydrogen bonding. Mineralogical Society of America - Geochemical Society Short Course “Molecular Modeling Theory: and Applications in the Geosciences”, Roanoke, VA, May 2001.
	A.G.Kalinichev (1998) Hydrogen bond dynamics in supercritical water. VIIth International Conference "Problems of solvation and complex formation in solutions", Ivanovo, Russia, p.462.
	A.G.Kalinichev (1997) Supercritical water as a medium for a new generation of environmentally friendly and energy efficient technologies of the XXI century (opening lecture). Moscow Seminar on Supercritical Fluids Science and Technology, Moscow, November 1997.
	A.G.Kalinichev (1996) Structute and Hydrogen Bonding in Liquid and Supercritical Water: Experimental Studies and Computer Simulations EMLG Annual Meeting "Structure and Thermodynamics of Solvents and Solutions". Balatonfured, Hungary, September 1996.