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Water dimer

About: Water dimer is a(n) research topic. Over the lifetime, 1159 publication(s) have been published within this topic receiving 88064 citation(s). more


Journal ArticleDOI: 10.1063/1.445869
Abstract: Classical Monte Carlo simulations have been carried out for liquid water in the NPT ensemble at 25 °C and 1 atm using six of the simpler intermolecular potential functions for the water dimer: Bernal–Fowler (BF), SPC, ST2, TIPS2, TIP3P, and TIP4P. Comparisons are made with experimental thermodynamic and structural data including the recent neutron diffraction results of Thiessen and Narten. The computed densities and potential energies are in reasonable accord with experiment except for the original BF model, which yields an 18% overestimate of the density and poor structural results. The TIPS2 and TIP4P potentials yield oxygen–oxygen partial structure functions in good agreement with the neutron diffraction results. The accord with the experimental OH and HH partial structure functions is poorer; however, the computed results for these functions are similar for all the potential functions. Consequently, the discrepancy may be due to the correction terms needed in processing the neutron data or to an effect uniformly neglected in the computations. Comparisons are also made for self‐diffusion coefficients obtained from molecular dynamics simulations. Overall, the SPC, ST2, TIPS2, and TIP4P models give reasonable structural and thermodynamic descriptions of liquid water and they should be useful in simulations of aqueous solutions. The simplicity of the SPC, TIPS2, and TIP4P functions is also attractive from a computational standpoint. more

Topics: Water model (53%), Solvent models (52%), Water dimer (51%) more

29,424 Citations

Journal ArticleDOI: 10.1063/1.445134
Alan E. Reed1, Frank Weinhold1Institutions (1)
Abstract: We have carried out a natural bond orbital analysis of hydrogen bonding in the water dimer for the near‐Hartree–Fock wave function of Popkie, Kistenmacher, and Clementi, extending previous studies based on smaller basis sets and less realistic geometry. We find that interactions which may properly be described as ‘‘charge transfer’’ (particularly the n‐σ*OH interaction along the H‐bond axis) play a critical role in the formation of the hydrogen bond, and without these interactions the water dimer would be 3–5 kcal/mol repulsive at the observed equilibrium distance. We discuss this result in relationship to Klemperer’s general picture of the bonding in van der Waals molecules, and to previous theoretical analyses of hydrogen bonding by the method of Kitaura and Morokuma. more

Topics: Water dimer (67%), Bond length (58%), Natural bond orbital (58%) more

2,392 Citations

Journal ArticleDOI: 10.1063/1.432402
Abstract: The potential energies for the water dimer in various geometrical configurations have been calculated with a configuration–interaction method. The computed dimerization binding energies corresponding to the potential minima for the linear, cyclic, and bifurcated configurations are −5.6, −4.9, and −4.2 kcal/mol, respectively; the correlation effects account for −1.1, −1.2, and −0.9 kcal/mol, respectively, of the total binding energy for these three dimeric forms. The correlation effects for the entire potential surface have been analyzed in terms of inter‐ and intramolecular effects; the substantial coupling found between these effects, particularly in the vicinity of equilibrium position, is discussed. The computational technique employed, in particular an analysis on the selection criteria for the configuration state functions, is discussed, and its reliability is assessed. Two analytical expressions for the water dimer potential surface obtained by fitting the calculated energies are presented. The potential surface given here is being used to determine the structure of liquid water (in the pairwise approximation and with Monte Carlo techniques); this latter work will be reported elsewhere. more

Topics: Water dimer (60%), Binding energy (50%)

1,085 Citations

Journal ArticleDOI: 10.1016/0009-2614(93)87156-W
Abstract: We use the resolution of the identify (RI) as convenient way to replace the use of four-index-two-electron integrals with linear combinations of three-index integrals. The method is broadly applicable to a wide range of problems in quantum chemistry. We demonstrate the effectivenes of RI for the calculation of MP2 energies. For the water dimer, agreement within 0.1 kcal/mol is obtained with respect to exact MP2 calculations. The RI-MP2 energies require only about 10% of the time required by conventional MP2. more

1,031 Citations

Journal ArticleDOI: 10.1063/1.462652
Abstract: A systematic series of calculations encompassing a wide range of basis sets and correlated methods has been used to estimate the complete basis set, full CI hydrogen bond strength in the water dimer system. The largest basis set included up through h polarization functions on oxygen and g functions on hydrogen. The complete basis set limit for the self‐consistent‐field (SCF) interaction energy is estimated to be −3.55 kcal/mol with an accompanying correlation contribution of ∼−1.5 kcal/mol. This leads to an interaction energy of −5.1 kcal/mol, exclusive of vibrational zero‐point considerations, and is in good agreement with experimental measurements of −5.4±0.7 kcal/mol. Inclusion of an approximate adjustment for the basis set superposition error via the Boys/Bernardi counterpoise correction was found to substantially improve agreement with ΔE∞, our estimate of the complete basis set interaction energy, at the both the SCF and correlated levels for basis sets that were lacking in sufficient near‐valence d... more

Topics: Quantum chemistry composite methods (59%), Interaction energy (57%), Water dimer (53%) more

996 Citations

No. of papers in the topic in previous years

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Topic's top 5 most impactful authors

Richard J. Saykally

23 papers, 1.7K citations

Krzysztof Szalewicz

12 papers, 1.2K citations

Hiroto Tachikawa

11 papers, 240 citations

Claude Leforestier

11 papers, 589 citations

Kwang S. Kim

10 papers, 376 citations

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