Abstract
A combined and sequential use of Monte Carlo simulation and quantum mechanics calculations is made to obtain the static dipole polarizability, and the related dielectric constant of atomic argon, in the liquid phase. Using Metropolis Monte Carlo simulation, within the NPT ensemble, the structure of liquid argon is obtained at T = 91.8 K and P = 1.8 atm. Seventy statistically relevant configurations are sampled for quantum mechanical calculations of the static dipole polarizability. Each configuration is composed of 14 Ar atoms, corresponding to the first solvation shell. Using these structures’ density-functional theory, calculations are performed within the B3P86 hybrid functional and the aug-cc-pVDZ basis set to obtain statistically converged values for the dipole polarizability. Three different models are used to extract the polarizability per atom. From the calculated density and dipole polarizability, the static dielectric constant is obtained using the simple Clausius-Mossotti relation. Our best result indicates a dipole polarizability of 11.6 a 30 and a dielectric constant of 1.52 in agreement with an experimentally available result of 1.53.
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References
O. Tapia, O. Goscinski, Self-consistent reaction field theory of solvent effects. Mol. Phys. 29, 1653–1661 (1975)
J.L. Rivail, D. Rinaldi, A quantum chemical approach to dielectric solvent effects on molecular liquids. Chem. Phys. 18, 233–242 (1976)
J. Tomasi, M. Persico, Molecular interactions in solutions: An overview of methods on continuous distribution of the solvents. Chem. Rev. 94, 2027–2094 (1994)
M.M. Karelson, M.C. Zerner, Theoretical treatment of solvent effects on electronic spectroscopy. J. Phys. Chem. 96, 6949–6957 (1992)
J. Tomasi, Thirty years of continuum solvation chemistry: A review, and prospect for the near future. Theor. Chem. Acc. 112, 184–203 (2004)
D.M. Heyes, The Liquid State. Applications of Molecular Simulations (Wiley, New York, 1998)
M.P. Allen, D.J. Tildesley, Computer Simulation of Liquids (Clarendon Press, Oxford 1987)
J.T. Blair, K. Krogh-Jespersen, R.M. Levy, Solvent effects on optical absorption spectra. The 1A1 → 1A2 transition of formaldehyde in water. J. Am. Chem. Soc. 111, 6948–6956 (1989)
J. Gao, Monte Carlo quantum mechanical-configuration interaction and molecular mechanics simulation of solvent effects on the n – π* blue shift of acetone. J. Am. Chem. Soc. 116, 9324–9328 (1994)
J. Zeng et al., Solvent effects on molecular spectra. I. Normal pressure and temperature Monte Carlo simulations of the structure of dilute pyrimidine in water. J. Chem. Phys. 99, 1482–1495 (1993)
K. Coutinho, S. Canuto, Solvent effects in emission spectroscopy: A Monte Carlo quantum mechanics study of the n – π* shift of formaldehyde in water. J. Chem. Phys. 113, 9132–9139 (2000)
K. Coutinho, S. Canuto, Solvent effects from a sequential Monte Carlo-quantum mechanics approach. Adv. Quantum Chem. 28, 89–105 (1997)
K. Coutinho et al., A Monte Carlo-quantum mechanics study of the solvatochromic shifts of the lowest transition of benzene. J. Chem. Phys. 112, 9874–9880 (2000)
H.C. Georg et al., Solvent effects on UV-visible absorption spectrum of benzophenone in water: A combined Monte Carlo quantum mechanics study including solute polarization. J. Chem. Phys. 126, 034507-1–034507-8 (2007)
T.S. Almeida et al., Electronic properties of liquid ammonia: A sequential molecular dynamicso/quantum mechanics approach. J. Chem. Phys. 128, 014506-1–014506-9 (2008)
A.D. Becke, Density-functional thermochemistry.III. The role of exact exchange. J. Chem. Phys. 98, 5648–5852 (1993)
J.P. Perdew, Density functional approximation for the correlation energy of the inhomogeneous electron gas. Phys. Rev. B 33, 8822–8824 (1986)
A. Morita, S. Kato, An ab initio analysis of medium perturbation on molecular polarizabilities. J. Chem. Phys. 110, 11987–11998 (1999)
K. Coutinho, S. Canuto, Sequential Monte Carlo/quantum mechanics study of the dipole polarizability of atomic liquids: The argon case, in Atoms, Molecules and Clusters in Electric Fields. Theoretical Approaches to the Calculation of Electric Polarizabilities, ed. by G. Maroulis (Imperial College Press, London, 2006), pp. 405–420
G.C. Maitland, E.B. Smith, The intermolecular pair potential of argon. Mol. Phys. 22, 861–868 (1971)
K. Coutinho, S. Canuto, DICE: A general Monte Carlo program for liquid simulation (University of São Paulo, Brazil (, 2000)
T. Malaspina et al., Ab initio calculation of hydrogen bonds in liquids: A sequential Monte Carlo quantum mechanics study of pyridine in water. J. Chem. Phys. 117, 1692–1699 (2002)
S. Canuto et al., New developments in Monte Carlo/quantum mechanics methodology. The solvatochromism of β-carotene in different solvents. Adv. Quantum Chem. 41, 161–183 (2002)
G. Maroulis, Static hyperpolarizability of the water dimer and the interaction hyperpolarizability of two water molecules. J. Chem. Phys. 113, 1813–1820 (2000)
K.V. Mikkelsen et al., Sign change of hyperpolarizabilities of solvated water. J. Chem. Phys. 102, 9362–9367 (1995)
S. Canuto et al., The dipole polarizability of F- in aqueous solution. A sequential Monte Carlo/quantum mechanics study. Adv. Quantum Chem. 48, 141–150 (2005)
F.B. van Duijneveldt et al., State of the art in counterpoise theory. Chem. Rev. 94, 1873–1885 (1994)
M.J. Frisch et al., Gaussian 98, Revision A.6, Gaussian, Inc. (Pittsburgh, PA, 1998)
A. Eisenstein, N.S. Gingrich, The diffraction of X-ray by argon in the liquid, vapor, and critical region. Phys. Rev. 62, 261–270 (1942)
C. Lupinetti, A.J. Thakkar, Polarizabilities and hyperpolarizabilities for the atoms, Al, Si, P, Cl and Ar:Coupled cluster calculations. J. Chem. Phys. 122, 44301-1–44301-7 (2005)
U. Hohm, K. Kerl, Interferometric measurement of the dipole polarizability of molecules between 300 K and 1100 K. Monochromatic measurements at λ = 632.99 nm for the noble gases and H2, N2, O2, and CH4. Mol. Phys. 69, 819–831 (1990)
D.R. Johnston et al., Dielectric constants of imperfect gases.I. Helium, argon, nitrogen, and methane. J. Chem. Phys. 33, 1310–1317 (1960)
R.J. Wheatley, Time-dependent coupled-cluster calculations of polarizabilities and dispersion energy coefficients. J. Comput. Chem. 29, 445–450 (2008)
H. Frölich, Theory of Dielectrics (Clarendon Press, Oxford, 1958)
D.R. Lide (ed), Handbook of Chemistry and Physics, 73rd edn. (CRC Press, Boca Raton, 1993), p. 9.51
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This work has been partially supported by CNPq, CAPES, and FAPESP (Brazil).
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Coutinho, K., Canuto, S. (2009). Sequential Monte Carlo and Quantum Mechanics Calculation of the Static Dielectric Constant of Liquid Argon. In: Leszczynski, J., Shukla, M. (eds) Practical Aspects of Computational Chemistry. Springer, Dordrecht. https://doi.org/10.1007/978-90-481-2687-3_16
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DOI: https://doi.org/10.1007/978-90-481-2687-3_16
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