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Optimized effective potentials from arbitrary basis sets
We investigate the use of a regularized optimized effective potential (OEP) energy functional and L-curve procedure [T. Heaton-Burgess, F. A. Bulat, and W. Yang, Phys. Rev. Lett. 98, 256401 (2007)] fo...

Precision shooting: Sampling long transition pathways

J. Chem. Phys. 129, 194101 (2008); doi:10.1063/1.2978000

Published 17 November 2008

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Michael Grünwald,1 Christoph Dellago,1 and Phillip L. Geissler2
1Faculty of Physics and Center for Computational Materials Science, University of Vienna, Boltzmanngasse 5, 1090 Vienna, Austria
2Department of Chemistry, University of California at Berkeley, Berkeley, California 94720, USA and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
The kinetics of collective rearrangements in solution, such as protein folding and nanocrystal phase transitions, often involve free energy barriers that are both long and rough. Applying methods of transition path sampling to harvest simulated trajectories that exemplify such processes is typically made difficult by a very low acceptance rate for newly generated trajectories. We address this problem by introducing a new generation algorithm based on the linear short time behavior of small disturbances in phase space. Using this “precision shooting” technique, arbitrarily small disturbances can be propagated in time, and any desired acceptance ratio of shooting moves can be obtained. We demonstrate the method for a simple but computationally problematic isomerization process in a dense liquid of soft spheres. We also discuss its applicability to barrier-crossing events involving metastable intermediate states. ©2008 American Institute of Physics
History: Received 14 July 2008; accepted 13 August 2008; published 17 November 2008
Permalink: http://link.aip.org/link/?JCPSA6/129/194101/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.30.Qt
    Isomerization and rearrangement in chemical reactions
  • 82.20.Wt
    Computational modeling and simulation of chemical kinetics
  • 82.20.Db
    Transition state theory and statistical theories of rate constants (chemical kinetics)
  • 82.20.Fd
    Collision theories and trajectory models of chemical kinetics
  • 82.20.Pm
    Chemical rate constants, reaction cross sections, and activation energies
  • YEAR: 2008

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (17)
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