TITLE

A global H2O potential energy surface for the reaction O(1D)+H2→OH+H

AUTHOR(S)
Ho, Tak-San; Hollebeek, Timothy; Rabitz, Herschel; Harding, Lawrence B.; Schatz, George C.
PUB. DATE
December 1996
SOURCE
Journal of Chemical Physics;12/15/1996, Vol. 105 Issue 23, p10472
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
A global, single-valued ground-state H2O potential surface for the reaction O(1D)+H2→OH+H has been constructed from a new set of accurate ab initio data using a general multidimensional interpolation method. The ab initio calculations are of the multireference, configuration interaction variety and were carried out using augmented polarized triple zeta basis sets. The multidimensional method is formulated within the framework of the reproducing kernel Hilbert space theory. The H2O potential is expressed as a many-body sum of a single one-body term, three two-body terms, and a single three-body term. The one-body term is the dissociation energy to the three-atom limit 2H(2S)+O(3P). The two-body terms are two O–H and one H–H adiabatic diatomic potentials of lowest energy. Each diatomic term is obtained by interpolating a discrete set of ab initio data using a one-dimensional, second-order, distancelike reproducing kernel. The three-body term is obtained by interpolating the difference of the H2O ab initio data and the one- and two-body sum by means of a direct product of three one-dimensional reproducing kernels on an optimized regular three-dimensional grid. The H2O potential energy surface is accurate, globally smooth, easy to evaluate, and asymptotically correct. Extensive quasiclassical trajectory calculations based on this new potential energy surface have been performed and compared with the results based on the potential energy surface of Murrell and Carter (MC) and that of Schinke and Lester (SL). Comparisons with recent experimental measurements on total cross sections, isotope effects, rate constants, vibrational, rotational, and angular distributions of the O(1D)+H2/HD reaction show that the new potential energy surface is a significant improvement over the MC and SL surfaces. © 1996 American Institute of Physics.
ACCESSION #
7629809

 

Related Articles

  • A global A-state potential surface for H[sub 2]O: Influence of excited states on the O([sup 1]D)... Schatz, George C.; Papaioannou, Anastasios; Pederson, Lisa A.; Harding, Lawrence B.; Hollebeek, Timothy; Tak-San Ho; Rabitz, Herschel // Journal of Chemical Physics;8/15/1997, Vol. 107 Issue 7, p2340 

    Presents a global potential energy surface for the A-state of H[sub 2]O based on application of the reproducing kernel Hilbert space interpolation method to high quality ab initio results. Use of the resulting surface to study the O([sup 1]D)+H[sub 2](HD,D[sub 2]) reaction dynamics; Reactive...

  • Rotational constants of all H/D substituted water trimers: Coupling of intermolecular torsional... Sabo, Dubravko; Bacic, Zlatko // Journal of Chemical Physics;3/22/1999, Vol. 110 Issue 12, p5745 

    Reports that a four-dimensional intermolecular potential energy surfaces for the water trimer was calculated in the subspace of the torsional coordinates and the symmetric intermolecular stretch coordinate. Quantum three-dimensional calculation of torsional levels of water trimers; Torsional...

  • Carbonyl–water hydrogen bonding: The H2CO–H2O prototype. Ramelot, Theresa A.; Hu, Ching-Han; Fowler, Joseph E.; DeLeeuw, Bradley J.; Schaefer, Henry F. // Journal of Chemical Physics;3/15/1994, Vol. 100 Issue 6, p4347 

    The potential energy surface (PES) of the water–formaldehyde complex has been examined using ab initio methods. Three energetically low-lying stationary points were located on the potential surface corresponding to one minimum and two transition states. All stationary points were examined...

  • Electron localization in liquid water: A computer simulation study of microscopic trapping sites. Schnitker, Jürgen; Rossky, Peter J.; Kenney-Wallace, Geraldine A. // Journal of Chemical Physics;9/1/1986, Vol. 85 Issue 5, p2986 

    Sites at which excess electrons in pure water at 10 °C could become initially localized and subsequently rapidly solvated are identified by scanning a molecular dynamics simulation of pure equilibrium ST2 water with a test charge. Very favorable sites with respect to both volume and...

  • The lower C2v potential energy surfaces of the singlet states of H2O: A computational study. Schneider, F.; Di Giacomo, F.; Gianturco, F. A. // Journal of Chemical Physics;4/1/1996, Vol. 104 Issue 13, p5153 

    We present here computational results on 15 C2v potential energy surfaces (PES) of H2O in its singlet state, while further results on the doublet state of the cation of the same system will be reported in a following paper. The PES are shown as 2D contour maps. Reaction pathways for symmetric...

  • An ab initio study of the torsional-puckering pseudorotation in the cyclic water pentamer. Graf, Stephan; Mohr, Wolfgang; Leutwyler, Samuel // Journal of Chemical Physics;4/22/1999, Vol. 110 Issue 16, p7893 

    The intermolecular potential energy surface and the torsional-puckering (TP) motion of the cyclic homodromic water pentamer were theoretically investigated at the level of second-order MoilerPlesset perturbation theory using double- and triple-zeta correlation-consistent basis sets including...

  • Six-dimensional quantum calculation of the intermolecular bound states for water dimer. Hua Chen; Liu, S.; Light, J.C. // Journal of Chemical Physics;1/1/1999, Vol. 110 Issue 1, p168 

    Presents results of six-dimensional bound-state calculations of the vibrations of rigid water dimer based on potential energy surfaces. Details of the calculations performed in Jacobi molecule-molecule collision coordinates; Integration of the potential; Diagonalization of the Hamiltonian.

  • Development of transferable interaction models for water. II. Accurate energetics of the first few water clusters from first principles. Xantheas, Sotiris S.; Burnham, Christian J.; Harrison, Robert J. // Journal of Chemical Physics;1/22/2002, Vol. 116 Issue 4, p1493 

    We report accurate energetics for the water trimer through pentamer global ring minima and four low-lying hexamer isomers (cage, prism, book, cyclic S[sub 6]) from first principles electronic structure calculations. The family of augmented correlation-consistent orbital basis sets of double...

  • A water dimer potential based on ab initio calculations using Morokuma component analyses. Singh, U. C.; Kollman, Peter A. // Journal of Chemical Physics;10/15/1985, Vol. 83 Issue 8, p4033 

    We present a new water dimer potential. It is based on carrying out Morokuma component analyses at the ab initio level on 229 water dimer geometries and fitting the energy components to analytical functional forms. To these are then added a dispersion contribution, based on the analytical...

Share

Read the Article

Courtesy of THE LIBRARY OF VIRGINIA

Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics