Artículos de revistas
Nuclear Quantum Fluctuations In Ice I<inf>h</inf>
Registro en:
Physical Chemistry Chemical Physics. Royal Society Of Chemistry, v. 17, n. 38, p. 24716 - 24721, 2015.
14639076
10.1039/c5cp03346b
2-s2.0-84942436354
Institución
Resumen
We discuss the role of nuclear quantum fluctuations in ice I<inf>h</inf>, focusing on the hydrogen-bond (HB) structure and the molecular dipole-moment distribution. For this purpose we carry out DFT-based first-principles molecular dynamics and path-integral molecular dynamics simulations at T = 100 K. We analyze the HB structure in terms of a set of parameters previously employed to characterize molecular structures in the liquid phase and compute the molecular dipole moments using the maximally-localized Wannier functions. The results show that the protons experience very large digressions driven by quantum fluctuations, accompanied by major rearrangements in the electronic density. As a result of these protonic quantum fluctuations the molecular dipole-moment distribution is substantially broadened as well as shifted to a larger mean value when compared to the results obtained when such fluctuations are neglected. In terms of dielectric constants, the reconciliation between the greater mean dipole moment and experimental indications that the dielectric constant of H<inf>2</inf>O ice is lower than that of D<inf>2</inf>O ice would indicate that the topology of the HB network is sensitive to protonic quantum fluctuations. This journal is © the Owner Societies. 17 38 24716 24721 Eisenberg, D., Kauzmann, W., (1969) The Structure and Properties of Water, , Oxford University Press, New York Petrenko, V.F., Whitworth, R.W., (1999) Physics of Ice, , Oxford University Press, New York Kawada, S., (1978) J. Phys. Soc. Jpn., 44, pp. 1881-1886 Johari, G.P., Jones, S.J., (1978) J. Glaciol., 21, p. 259 Takei, I., Maeno, N., (1987) J. Phys., 48, p. 121. , C1 Aragones, J.L., MacDowell, L.G., Vega, C., (2011) J. Phys. Chem. A, 115, pp. 5745-5758 Schönherr, M., Slater, B., Hutter, J., VandeVondele, J., (2014) J. Phys. Chem. B, 118, pp. 590-596 Johari, G.P., Whalley, E., (1981) J. Chem. Phys., 75, pp. 1333-1340 Rahman, A., Stillinger, F.H., (1972) J. Chem. Phys., 57, pp. 4009-4017 Barkema, G.T., De Boer, J., (1993) J. Chem. Phys., 99, pp. 2059-2067 Buch, V., Sandler, P., Sadlej, J., (1998) J. Phys. Chem. B, 102, pp. 8641-8653 Rick, S.W., Haymet, A.D.J., (2003) J. Chem. Phys., 118, pp. 9291-9296 Lindberg, G.E., Wang, F., (2008) J. Phys. Chem. B, 112, pp. 6436-6441 MacDowell, L.G., (2010) J. Phys. Chem. B, 114, p. 6089 Rusnak, A.J., Pinnick, E.R., Calderon, F., Camilo, E., (2012) J. Chem. Phys., 137, p. 034510 Nagle, J.F., (1974) J. Chem. Phys., 61, pp. 883-888 Hirsch, T.K., Ojamäe, L., (2004) J. Phys. Chem. B, 108, pp. 15856-15864 Marx, D., Hütter, J., (2009) Ab Initio Molecular Dynamics: Basic Theory and Advanced Methods, , Cambridge University Press Chen, B., Ivanov, I., Klein, M.L., Parrinello, M., (2003) Phys. Rev. Lett., 91, p. 215503 Morrone, J.A., Car, R., (2008) Phys. Rev. Lett., 101, p. 017801 Ramírez, R., Herrero, C.P., (2010) J. Chem. Phys., 133, p. 144511 Li, X.-Z., Walker, B., Michaelides, A., (2011) Proc. Natl. Acad. Sci. U. S. A., 108, pp. 6369-6373 Pamuk, B., Soler, J.M., Ramírez, R., Herrero, C.P., Stephens, P.W., Allen, P.B., Fernández-Serra, M.-V., (2012) Phys. Rev. Lett., 108, p. 193003 Ceriotti, M., Cuny, J., Parrinello, M., Manolopoulos, D.E., (2013) Proc. Natl. Acad. Sci. U. S. A., 110, pp. 15591-15596 Drechsel-Grau, C., Marx, D., (2014) Phys. Rev. Lett., 112, p. 148302 Drechsel-Grau, C., Marx, D., (2014) Angew. Chem., Int. Ed., 53, pp. 10937-10940 Fritsch, S., Potestio, R., Donadio, D., Kremer, K., (2014) J. Chem. Theory Comput., 10, pp. 816-824 Hayward, J.A., Reimers, J.R., (1997) J. Chem. Phys., 106, pp. 1518-1529 CPMD, Copyright IBM Corp 1990-2008, 1997-2001, Copyright MPI für Festkörperforschung StuttgartTroullier, N., Martins, J.L., (1991) Phys. Rev. B: Condens. Matter Mater. Phys., 43, pp. 1993-2006 Perdew, J.P., Burke, K., Ernzerhof, M., (1996) Phys. Rev. Lett., 77, pp. 3865-3868 Becke, A.D., (1988) Phys. Rev. A: At., Mol., Opt. Phys., 38, pp. 3098-3100 Lee, C., Yang, W., Parr, R.G., (1988) Phys. Rev. B: Condens. Matter Mater. Phys., 37, pp. 785-789 Nosé, S., (1984) J. Chem. Phys., 81, pp. 511-519 Hoover, W.G., (1985) Phys. Rev. A: At., Mol., Opt. Phys., 31, pp. 1695-1697 Car, R., Parrinello, M., (1985) Phys. Rev. Lett., 55, pp. 2471-2474 Martyna, G.J., Tobias, D.J., Klein, M.L., (1994) J. Chem. Phys., 101, pp. 4177-4189 Marzari, N., Mostofi, A.A., Yates, J.R., Souza, I., Vanderbilt, D., (2012) Rev. Mod. Phys., 84, pp. 1419-1475 Kawada, S., (1979) J. Phys. Soc. Jpn., 47, pp. 1850-1856 Johari, G.P., Jones, S.J., (1976) Proc. R. Soc. A, 349, pp. 467-495