Predictions of the Properties of Water from First Principles

Bukowski, Robert; Szalewicz, Krzysztof; Groenenboom, Gerrit C.; Avoird, Ad van der

doi:10.1126/science.1136371

Cited by 396 publications

(339 citation statements)

References 34 publications

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“…Calculations on the effects of monomer flexibility [18][19][20] have shown that this quantity a͑0͒ + a͑1͒ decreases when the H 2 O monomers are relaxed. It is striking in this respect, see Table VI, that the other pure ab initio potential that gives very good agreement with the experimental data, the 6D CC-pol potential, 10,17,21 gives practically the same deviation from experiment for a͑0͒ + a͑1͒ as the HBB0 and HBB potentials. It is most probable that all of these potentials have reached the "rigid monomer limit" of the acceptor splitting.…”

Section: Vibration-rotation Tunneling Spectrum Of the Water Dimersupporting

confidence: 66%

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New ab initio potential energy surface and the vibration-rotation-tunneling levels of (H2O)2 and (D2O)2

Huang

Braams

Bowman

et al. 2008

The Journal of Chemical Physics

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112

139

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We report a new full-dimensional potential energy surface ͑PES͒ for the water dimer, based on fitting energies at roughly 30 000 configurations obtained with the coupled-cluster single and double, and perturbative treatment of triple excitations method using an augmented, correlation consistent, polarized triple zeta basis set. A global dipole moment surface based on Møller-Plesset perturbation theory results at these configurations is also reported. The PES is used in rigorous quantum calculations of intermolecular vibrational frequencies, tunneling splittings, and rotational constants for ͑H 2 O͒ 2 and ͑D 2 O͒ 2 , using the rigid monomer approximation. Agreement with experiment is excellent and is at the highest level reported to date. The validity of this approximation is examined by comparing tunneling barriers within that model with those from fully relaxed calculations.

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Section: Vibration-rotation Tunneling Spectrum Of the Water Dimersupporting

confidence: 66%

“…There has been great progress in realizing this goal recently. 10 Here, we report additional and significant progress in this effort.…”

Section: Introductionmentioning

confidence: 99%

New ab initio potential energy surface and the vibration-rotation-tunneling levels of (H2O)2 and (D2O)2

Huang

Braams

Bowman

et al. 2008

The Journal of Chemical Physics

Self Cite

112

139

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show abstract

“…This shows that the new excited A-E state wave functions are more localized than are the ground state A-E wave functions. Olthof et al 12 calculated the splittings due to umbrella inversion of the para monomer in the ammonia …”

Section: Discussionmentioning

confidence: 99%

“…Nevertheless, we hope that the present study will motivate detailed study of the ammonia dimer by a similar combination of state of the art dynamics and potential models, such as the ones recently published for the water dimer. 10,12 This would greatly accelerate our understanding of this important prototype system. The internal coordinate system of the ammonia dimer.…”

Section: Methodsmentioning

confidence: 97%

Terahertz Vibration−Rotation−Tunneling Spectroscopy of the Ammonia Dimer. II. A−E States of an Out-of-Plane Vibration and an In-Plane Vibration

et al. 2007

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Terahertz vibration-rotation-tunneling transitions have been measured between ca. 78.5 and 91.9 cm -1 , and assigned to A-E (ortho-para) combinations of NH 3 monomer states. The spectrum is complicated by inversion splittings that correlate to E symmetry monomer rovibronic states. Twenty progressions have been assigned to six excited states involving an out-of-plane vibration and an in-plane intermolecular vibration. The quality of the fit was affected by strong Coriolis interactions among these states and possibly an additional K ) 2 state that was not explicitly observed in the data.

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“…Reference 25 reviews the work up to the year 2000. Several ab initio water pair potentials have been obtained recently, with [26][27][28][29] or without 30,31 explicit inclusion of the polarization effects that form the dominant contribution to the many-body interactions in water. These water pair potentials were tested by a computation 29,31 of the vibration-rotation-tunneling ͑VRT͒ levels of the water dimer and comparison with the available high-resolution terahertz spectra.…”

Section: Introductionmentioning

confidence: 99%

Water trimer torsional spectrum from accurate ab initio and semiempirical potentials

Avoird

Szalewicz

2008

The Journal of Chemical Physics

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The torsional levels of ͑H 2 O͒ 3 and ͑D 2 O͒ 3 were calculated in a restricted dimensionality ͑three-dimensional͒ model with several recently proposed water potentials. Comparison with the experimental data provides a critical test, not only of the pair interactions that have already been probed on the water dimer spectra, but also of the nonadditive three-body contributions to the potential. The purely ab initio CC-pol and HBB potentials that were previously shown to yield very accurate water dimer levels, also reproduce the trimer levels well when supplemented with an appropriate three-body interaction potential. The TTM2.1 potential gives considerably less good agreement with experiment. Also the semiempirical VRT͑ASP-W͒III potential, fitted to the water dimer vibration-rotation-tunneling levels, gives substantial disagreement with the measured water trimer levels, which shows that the latter probe the potential for geometries other than those probed by the dimer spectrum. Although the three-body nonadditive interactions significantly increase the stability of the water trimer, their effect on the torsional energy barriers and vibration-tunneling frequencies is less significant.

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Predictions of the Properties of Water from First Principles

Cited by 396 publications

References 34 publications

New ab initio potential energy surface and the vibration-rotation-tunneling levels of (H2O)2 and (D2O)2

New ab initio potential energy surface and the vibration-rotation-tunneling levels of (H2O)2 and (D2O)2

Terahertz Vibration−Rotation−Tunneling Spectroscopy of the Ammonia Dimer. II. A−E States of an Out-of-Plane Vibration and an In-Plane Vibration

Water trimer torsional spectrum from accurate ab initio and semiempirical potentials

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