First-row hydrides: Dissociation and ground state energies using quantum Monte Carlo

Lüchow, Arne; Anderson, James B.
November 1996
Journal of Chemical Physics;11/1/1996, Vol. 105 Issue 17, p7573
Academic Journal
Accurate ground state energies comparable to or better than the best previous ab initio results can be obtained using the fixed-node quantum Monte Carlo (FN-DQMC) method. The residual energy, the nodal error due to the error in the nodal structure of a trial wave function, is examined in this study using nodal surfaces given by near HF-limit wave functions. The study is aimed at better understanding of the nodal error and the cancellation of nodal errors in calculating energy differences. Calculations have been carried out for the first-row hydrides LiH to FH and the corresponding atoms. The FN-DQMC ground state energies are among the lowest to date. The dissociation energies De have been calculated with accuracies of 0.5 kcal mol-1 or better. For all hydrides, the dissociation energies are consistent with experimental values. The fixed-node quantum Monte Carlo method can therefore offer a very straight-forward way to calculate highly accurate dissociation energies. © 1996 American Institute of Physics.


Related Articles

  • Monte Carlo study of kinetic smoothing during dissolution and etching of the Kossel (100) and silicon (111) surfaces. Veenendaal, E. van; van Beurden, P.; van Enckevort, W. J. P.; Vlieg, E.; van Suchtelen, J.; Elwenspoek, M. // Journal of Applied Physics;10/15/2000, Vol. 88 Issue 8, p4595 

    Analyzes the asymmetry between growth and dissociation using Monte Carlo simulations of flat and vicinal surfaces of a Kossel crystal. Production of very anisotropic and nearly anatomically flat surfaces at a high driving force dissolution; Role of the chemical-etch reaction in determining the...

  • Trajectory studies of OH vibrational excitation propensities in the reaction of O(1D) with H2. Goldfield, Evelyn M.; Wiesenfeld, John R. // Journal of Chemical Physics;7/15/1990, Vol. 93 Issue 2, p1030 

    The reaction of excited oxygen atoms with hydrogen molecules has been explored using classical trajectory methods, with particular emphasis on those features of the dynamics responsible for the OH vibrational distribution. Plots of final OH vibrational action vs. initial H2 phase are analyzed. A...

  • Quantum Monte Carlo calculations of the dissociation energies of three-electron hemibonded radical cationic dimers. Gurtubay, I. G.; Drummond, N. D.; Towler, M. D.; Needs, R. J. // Journal of Chemical Physics;1/14/2006, Vol. 124 Issue 2, p024318 

    We report variational and diffusion quantum Monte Carlo (VMC and DMC) calculations of the dissociation energies of the three-electron hemibonded radical cationic dimers of He, NH3, H2O, HF, and Ne. These systems are particularly difficult for standard density-functional methods such as the...

  • Accuracy of electronic wave functions in quantum Monte Carlo: The Effect of high-order correlations. Chien-Jung Huang; Umrigar, C.J.; Nightingale, M.P. // Journal of Chemical Physics;8/22/1997, Vol. 107 Issue 8, p3007 

    Discusses how compact and accurate wave functions can be constructed by quantum Monte Carlo methods. Importance of including high-order, nucleus-three-electron correlations in the Jastrow factor; Computation of high-body correlations; Improvements in the variational Monte Carlo energy; Ground...

  • Relativistic effective potentials in quantum Monte Carlo calculations. Hurley, M. M.; Christiansen, P. A. // Journal of Chemical Physics;1/15/1987, Vol. 86 Issue 2, p1069 

    The frozen-core approximation was introduced into quantum Monte Carlo calculations by means of relativistic effective potentials. The conventional semilocal effective potentials were converted to local form using the same trial wave function used for importance sampling. Test calculations on Li,...

  • Semiclassical initial value approach for chaotic long-lived dynamics. Campolieti, G.; Brumer, Paul // Journal of Chemical Physics;8/22/1998, Vol. 109 Issue 8, p2999 

    Presents the stationary phase Monte Carlo method for wave function propagation. Discussion of the initial value representation (IVR) formula; Effect of chaotic systems on the implementation of IVR methods; Application of the quartic oscillator.

  • Construction of simulation wave functions for aqueous species: D[sub 3]O[sup +]. Gomez, M.A.; Pratt, L.R. // Journal of Chemical Physics;11/22/1998, Vol. 109 Issue 20, p8783 

    Investigates the Monte Carlo techniques for the construction of compact wave functions for the internal atomic motion of the D[sub 3]O[sup +] ion. Generation of the initial pair product wave functions; Characteristics of the pair product wave functions; Determination of accuracy and...

  • A spline approach to trial wave functions for variational and diffusion Monte Carlo. Bressanini, Dario; Fabbri, Giordano; Mella, Massimo; Morosi, Gabriele // Journal of Chemical Physics;10/8/1999, Vol. 111 Issue 14, p6230 

    Describes how to combine the variational Monte Carlo method with a spline approach of the wave function to obtain a powerful and flexible method to optimize electronic and nuclear wave functions. Main properties of spline functions; Brief summary of the Monte Carlo algorithm; Computation of the...

  • Optimization of quantum Monte Carlo wave functions using analytical energy derivatives. Lin, Xi; Zhang, Hongkai; Rappe, Andrew M. // Journal of Chemical Physics;2/8/2000, Vol. 112 Issue 6 

    An algorithm is proposed to optimize quantum Monte Carlo (QMC) wave functions based on Newton's method and analytical computation of the first and second derivatives of the variational energy. This direct application of the variational principle yields significantly lower energy than variance...


Read the Article


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

Try another library?
Sign out of this library

Other Topics