‘‘<i>Ab</i> <i>initio</i>’’ liquid water

Laasonen, Kari; Sprik, Michiel; Parrinello, Michele; Car, Roberto

doi:10.1063/1.465574

Cited by 606 publications

(435 citation statements)

References 66 publications

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“…BLYP functional has been shown to be able to accurately describe the behaviors of water and protons (e.g. Laasonen, 1993;Marx et al, 1999). This functional can also nicely predict free energy changes of proton transfer processes in aqueous systems (e.g.…”

Section: Car-parrinello MDmentioning

confidence: 99%

Atomic scale structures of interfaces between kaolinite edges and water

Liu

Wang

et al. 2012

Geochimica et Cosmochimica Acta

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This paper reports the atomic scale structures of kaolinite edge surfaces in contact with water. The commonly occurring edge surfaces are investigated (i.e. (0 1 0) and (1 1 0)) by using first principles molecular dynamics (FPMD) technique. For (1 1 0)-type edge surface, there are two different surface topologies (denoted as (1 1 0)-1 and (1 1 0)-2) and they are considered separately.By using constrained FPMD technique, the free-energy changes for the leaving processes of water ligands of O-sheet Al cations have been calculated and thus, the coordination states of those Al cations are determined. The results show that for (0 1 0) and (1 1 0)-2 edges, both the 5 and 6-fold coordination states are possible whereas for (1 1 0)-1 edges, only the 6-fold states are stable. Based on the analyses of H-bonding structures at the interfaces, the surface acid/base reactive sites are illustrated. (1) T-sheet groups are "Si-OH, behaving as both proton donors and acceptors. (2) Bridging oxygen At (0 1 0) and (1 1 0)-2 edges, these sites are inaccessible from the water and thus, they are not effective reactive sites. At (1 1 0)-1 edges, the bridging oxygen atoms are proton accepting sites. (3) O-sheet groups At (0 1 0) and (1 1 0)-2 edges, for 6-fold Al cases, the active surface groups are "Al-(OH)(OH 2 ) and for the 5-fold Al cases, the active surface groups are "Al-(OH). At (1 1 0)-1 edges, the active site is "Al-OH 2 . This study provides fundamental structural properties for understanding the interface chemistry of widely occurring 1:1 type phyllosilicates.

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Section: Car-parrinello MDmentioning

confidence: 99%

Atomic scale structures of interfaces between kaolinite edges and water

Liu

Wang

et al. 2012

Geochimica et Cosmochimica Acta

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14] The DFT methods are more economical, and the use of molecular dynamics and Monte Carlo methods to study bulk water [15][16][17][18][19][20][21][22][23] has placed an increased importance on finding a density functional method that can accurately describe these systems. While a recent advance 25 has allowed for the inclusion of Hartree-Fock exchange into the plane wave code VASP, 26 many of the simulation methods that employ plane waves 15 require the use of a density functional method that does not contain any Hartree-Fock exchange, that is, a nonhybrid method. (A hybrid functional contains HartreeFock exchange, hybrid meta functionals contain Hartree-Fock exchange and kinetic energy density, and generalized gradient approximations (GGAs) and local spin density approximations (LSDAs) contain neither.)…”

Section: Introductionmentioning

confidence: 99%

Improved Density Functionals for Water

2005

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The accuracy of existing density functional methods for describing the noncovalent interaction energies in small water clusters is investigated by testing 25 density functionals against a data set of 28 water dimers and 8 water trimers whose structures are taken from the literature and from simulations. The most accurate functionals are found to be PW6B95 with a mean unsigned error of 0.13 kcal/mol and MPWB1K and B98 with mean unsigned errors of 0.15 kcal/mol; the best functional with no Hartree-Fock exchange is mPWLYP, which is a GGA with a mean unsigned error of 0.28 kcal/mol. In comparison, the most popular GGA functionals, PBE and BLYP, have mean unsigned errors of 0.52 and 1.03 kcal/mol, respectively. Since GGAs are very cost efficient for both condensed-phase simulations and electronic structure calculations on large systems, we optimized four new GGAs for water. The best of these, PBE1W and MPWLYP1W, have mean unsigned errors of 0.12 and 0.17 kcal/mol, respectively. These new functionals are well suited for use in condensed-phase simulations of water and ice.

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“…Density functional theory (DFT) is the most used quantum mechanical method employed for studying physical and chemical properties of condensed phase systems. Many DFT based simulation of bulk water have been reported in the literature, and in this context three main methods of sampling the phase space can be recognized 14 : the Car-Parrinello molecular dynamics (CPMD) and related variants [15][16][17][18][19][20][21] , Born-Oppenheimer molecular dynamics (BOMD) [22][23][24][25][26] and Monte Carlo (MC) sampling. 27 Most of the CPMD and BOMD simulations were carried out in either the microcanonical (NVE) or canonical (NVT) ensemble by constraining the volume to reproduce the experimental density ρ.…”

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confidence: 99%

Bulk Liquid Water at Ambient Temperature and Pressure from MP2 Theory

Ben

Schönherr

Hutter

et al. 2013

J. Phys. Chem. Lett.

138

112

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MP2 provides a good description of hydrogen bonding in water clusters and includes longrange dispersion interactions without the need to introduce empirical elements in the description of the interatomic potential. To assess its performance for bulk liquid water under ambient conditions, an isobaric-isothermal (NpT) Monte Carlo simulation at the second-order Moller-Plesset perturbation theory level (MP2) has been performed. The obtained value of the water density is excellent (1.02 g/mL), and the calculated radial distribution functions are in fair agreement with experimental data. The MP2 results are compared to a few density functional approximations, including semilocal functionals, hybrid functionals, and functionals including empirical dispersion corrections. These results demonstrate the feasibility of directly sampling the potential energy surface of condensed-phase systems using correlated wave function theory, and their quality paves the way for further applications. Understanding the structural and electronic properties of liquid water at ambient conditions is a major challenge in condensed matter simulations. Water is a crucial ingredient for a large variety of systems of prime importance in basic chemistry, biology, and physics, as well as in the applied fields of catalysis and energy production. The water molecule has a large dipole moment and polarizability, is a multiple hydrogen donor and acceptor and can easily build network structures.The total cohesive energy in the condensed phase is, as a consequence of these properties, a sum of many weak interactions. Theoretical models face therefore the challenge to describe many different effects and their subtle interplay at a high precision. The development of sophisticated empirical potentials for water 1-10 , allowed to gain insights into water's behavior and its thermodynamic properties [11][12][13] , such as, density maxima, heat capacity and effects of supercooling. However, empirical models lack transferability and might fail if used under conditions away from their fitting range. Most importantly, as soon as water takes an active role in a chemical process, either as a strongly interacting solvent, or for example as a source of protons, the electronic properties of the water molecule need to be taken into account. In this respect, first-principles methods offer the possibility to describe all the underlying physics on the same footing, simplifying the treatment of intra-and inter-molecular interactions. The capability to reproduce properties of complex systems such as liquid water can therefore be used to judge the sophistication and predictive power of a given quantum mechanical model. Density functional theory (DFT) is the most used quantum mechanical method employed for studying physical and chemical properties of condensed phase systems. Many DFT based simulation of bulk water have been reported in the literature, and in this context three main methods of sampling the phase space can be recognized 14 : the Car-Parrinello molecula...

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‘‘Ab initio’’ liquid water

Cited by 606 publications

References 66 publications

Atomic scale structures of interfaces between kaolinite edges and water

Atomic scale structures of interfaces between kaolinite edges and water

Improved Density Functionals for Water

Bulk Liquid Water at Ambient Temperature and Pressure from MP2 Theory

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