Abstract
We present results from an ab initio molecular dynamics study of pure water. Using the resources available at the HLRB2 we were able to produce the first trajectories of sufficient length and number, that allow to study dynamical processes on the picosecond timescale with statistically reliable results. Additionally we computed a statistically converged infrared absorption spectrum from 0–4000 cm−1, which is in good agreement with the experimental observation. In particular, at THz frequencies the spectra qualitatively reproduce important features, whereas, in contrast, force field based simulations have been shown to utterly fail. In order to compensate for the neglect of quantum effects for the nuclei in classical dynamics simulations on an ab initio potential energy surface and potential overbinding in conjunction with the used electron structure method, we applied an increased intrinsic temperature of 400K in order to obtain structural and dynamical properties corresponding to an experimental temperature of 300K.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Ball P (2008) Water as an Active Constituent in Cell Biology. Chem Rev 108:74–108
Bagchi B (2005) Water Dynamics in the Hydration Layer around Proteins and Micelles. Chem Rev 105:3197–3219
Becke AD (1988) Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A 38:3098–3100
Bertie JE, Lan Z (1996) Infrared Intensities of Liquids XX: The Intensity of the OH Stretching Band of Liquid Water Revisited, and the Best Current Values of the Optical Constants of H2O(l) at 25°C between 15,000 and 1 cm−1. Appl Spec 50:1047–1057
Ebbinghaus S, Kim SJ, Heyden M, Yu X, Heugen U, Gruebele M, Leitner DM, Havenith M (2007) An extended dynamical hydration shell around proteins. Proc Natl Acad Sci 104:20749–20752
Ebbinghaus S, Kim SJ, Heyden M, Yu X, Gruebele M, Leitner DM, Havenith M (2008) Protein Sequence- and pH-Dependent Hydration Probed by Terahertz Spectroscopy. J Am Chem Soc 130:2374–2375
Fanourgakis GS, Xantheas SS (2008) Development of transferable interaction potentials for water. V. Extension of the flexible, polarizable, Thole-type model potential (TTM3-F, v. 3.0) to describe the vibrational spectra of water clusters and liquid water. J Chem Phys 128:074506
Fernández-Serra MV, Artacho E (2004) Network equilibration and first-principles liquid water. J Cehm Phys 121:11136–11144
Goedecker S, Teter M, Hutter J (1996) Separable dual-space Gaussian pseudopotentials. Phys Rev B 54:1703–1710
Grossman JC, Schwegler E, Draeger EW, Gygi F, Galli G (2004) Towards an assessment of the accuracy of density functional theory for first principles simulations of water. J Chem Phys 120:300–311
Hartwigsen C, Goedecker S, Hutter J (1998) Relativistic separable dual-space Gaussian pseudopotentials from H to Rn. Phys Rev B 58:3641–3662
Hertz HG (1973) Nuclear magnetic relaxation spectroscopy. In Water: A Comprehensive Treatise, Vol. 3. F. Franks, editor. Plenum Press, New York 301–395.
Heugen U, Schwaab G, Bründermann E, Heyden M, Yu X, Leitner DM, Havenith M (2006) Solute-induced retardation of water dynamics probed directly by terahertz spectroscopy. Proc Natl Acad Sci 103:12301–12306
Heyden M, Niehues G, Heugen U, Leitner DM, Havenith M (2008) The long range influence of carbohydrates on the solvation dynamics of water - answers from THz spectroscopic measurements and molecular modelling simulations. J Am Chem Soc 130:5773–5779
Kohn W, Sham LJ (1965) Self-Consistent Equations Including Exchange and Correlation Effects. Phys Rev 140:A1133–A1138
Kim SJ, Born B, Havenith M, Gruebele M (2008) Real-Time Detection of Protein-Water Dynamics upon Protein Folding by Terahertz Absorption Spectroscopy. Angew Chem Int Ed 47:6486–6489
Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789
Marx D, Hutter J (2009) Ab initio Molecular Dynamics - Basic Theory and Advanced Methods. Cambridge University Press
Marzari N, Vanderbilt D (1997) Maximally localized generalized Wannier functions for composite energy bands. Phys Rev B 56:12847–12865
Pal SK, Peon J, Bagchi B, Zewail AH (2002) Biological Water: Femtosecond Dynamics of Macromolecular Hydration. J Phys Chem B 106:12376–12395
Perdew JP, Burke K, Ernzerhof M, (1996) Generalized Gradient Approximation Made Simple. Phys Rev Lett 108:74–108
Rahman A, Stillinger FH (1974) Propagation of sound in water. A molecular-dynamics study. Phys Rev A 10:368–378
RamÃrez R, López-Ciudad T, Kumar P, Marx D (2004) Quantum corrections to classical time-correlation functions: Hydrogen bonding and anharmonic floppy modes. J Chem Phys 121:3973–3983
Schwegler E, Grossman JC, Gygi F, Galli G (2004) Towards an assessment of the accuracy of density functional theory for first principles simulations of water. II. J Chem Phys 121:5400–5409
Sharma M, Resta R, Car R (2005) Intermolecular Dynamical Charge Fluctuations in Water: AÂ Signature of the H-Bond Network. Phys Rev Lett 95:187401
Silvestrelli PL, Bernasconi M, Parrinello M (1997) Ab initio infrared spectrum of liquid water. Chem Phys Lett 277:478–482
Soper AK (2000) The radial distribution functions of water and ice from 220 to 673 K and at pressures up to 400 MPa. Chem Phys 258:121–137
VandeVondele J, Krack M, Mohamed F, Parrinello M, Chassaing T, Hutter J (2005) Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach. Comput Phys Commun 167:103–128
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2010 Springer-Verlag Berlin Heidelberg
About this paper
Cite this paper
Heyden, M., Havenith, M. (2010). Statistically Converged Properties of Water from Ab Initio Molecular Dynamics Simulations. In: Wagner, S., Steinmetz, M., Bode, A., Müller, M. (eds) High Performance Computing in Science and Engineering, Garching/Munich 2009. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-13872-0_57
Download citation
DOI: https://doi.org/10.1007/978-3-642-13872-0_57
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-13871-3
Online ISBN: 978-3-642-13872-0
eBook Packages: Mathematics and StatisticsMathematics and Statistics (R0)