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Title: Direct Dynamics Simulations using Hessian-based Predictor-corrector Integration Algorithms

Abstract

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. In previous research (J. Chem. Phys. 111, 3800 (1999)) a Hessian-based integration algorithm was derived for performing direct dynamics simulations. In the work presented here, improvements to this algorithm are described. The algorithm has a predictor step based on a local second-order Taylor expansion of the potential in Cartesian coordinates, within a trust radius, and a fifth-order correction to this predicted trajectory. The current algorithm determines the predicted trajectory in Cartesian coordinates, instead of the instantaneous normal mode coordinates used previously, to ensure angular momentum conservation. For the previous algorithm the corrected step was evaluated in rotated Cartesian coordinates. Since the local potential expanded in Cartesian coordinates is not invariant to rotation, the constants of motion are not necessarily conserved during the corrector step. An approximate correction to this shortcoming was made by projecting translation and rotation out of the rotated coordinates. For the current algorithm unrotated Cartesian coordinates are used for the corrected step to assure the constants ofmore » motion are conserved. An algorithm is proposed for updating the trust radius to enhance the accuracy and efficiency of the numerical integration. This modified Hessian-based integration algorithm, with its new components, has been implemented into the VENUS/NWChem software package and compared with the velocity-Verlet algorithm for the H₂CO→H₂+CO, O₃+C₃H₆, and F -+CH₃OOH chemical reactions.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
921827
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 126; Journal Issue: 4
Country of Publication:
United States
Language:
English
Subject:
99 GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE; ACCURACY; ALGORITHMS; ANGULAR MOMENTUM; CARTESIAN COORDINATES; CHEMICAL REACTIONS; EFFICIENCY; ROTATION; TRAJECTORIES; Environmental Molecular Sciences Laboratory

Citation Formats

Lourderaj, Upakarasamy, Song, Kihyung, Windus, Theresa L, Zhuang, Yu, and Hase, William L. Direct Dynamics Simulations using Hessian-based Predictor-corrector Integration Algorithms. United States: N. p., 2007. Web. doi:10.1063/1.2437214.
Lourderaj, Upakarasamy, Song, Kihyung, Windus, Theresa L, Zhuang, Yu, & Hase, William L. Direct Dynamics Simulations using Hessian-based Predictor-corrector Integration Algorithms. United States. doi:10.1063/1.2437214.
Lourderaj, Upakarasamy, Song, Kihyung, Windus, Theresa L, Zhuang, Yu, and Hase, William L. Mon . "Direct Dynamics Simulations using Hessian-based Predictor-corrector Integration Algorithms". United States. doi:10.1063/1.2437214.
@article{osti_921827,
title = {Direct Dynamics Simulations using Hessian-based Predictor-corrector Integration Algorithms},
author = {Lourderaj, Upakarasamy and Song, Kihyung and Windus, Theresa L and Zhuang, Yu and Hase, William L},
abstractNote = {The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. In previous research (J. Chem. Phys. 111, 3800 (1999)) a Hessian-based integration algorithm was derived for performing direct dynamics simulations. In the work presented here, improvements to this algorithm are described. The algorithm has a predictor step based on a local second-order Taylor expansion of the potential in Cartesian coordinates, within a trust radius, and a fifth-order correction to this predicted trajectory. The current algorithm determines the predicted trajectory in Cartesian coordinates, instead of the instantaneous normal mode coordinates used previously, to ensure angular momentum conservation. For the previous algorithm the corrected step was evaluated in rotated Cartesian coordinates. Since the local potential expanded in Cartesian coordinates is not invariant to rotation, the constants of motion are not necessarily conserved during the corrector step. An approximate correction to this shortcoming was made by projecting translation and rotation out of the rotated coordinates. For the current algorithm unrotated Cartesian coordinates are used for the corrected step to assure the constants of motion are conserved. An algorithm is proposed for updating the trust radius to enhance the accuracy and efficiency of the numerical integration. This modified Hessian-based integration algorithm, with its new components, has been implemented into the VENUS/NWChem software package and compared with the velocity-Verlet algorithm for the H₂CO→H₂+CO, O₃+C₃H₆, and F-+CH₃OOH chemical reactions.},
doi = {10.1063/1.2437214},
journal = {Journal of Chemical Physics},
number = 4,
volume = 126,
place = {United States},
year = {Mon Jan 29 00:00:00 EST 2007},
month = {Mon Jan 29 00:00:00 EST 2007}
}