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Title: Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol

Finding transition paths for chemical reactions can be computationally costly owing to the level of quantum-chemical theory needed for accuracy. Here, we show that a multilevel preconditioning scheme that was recently introduced (Tempkin et al. J. Chem. Phys. 2014, 140, 184114) can be used to accelerate quantum-chemical string calculations. We demonstrate the method by finding minimum-energy paths for two well-characterized reactions: tautomerization of malonaldehyde and Claissen rearrangement of chorismate to prephanate. For these reactions, we show that preconditioning density functional theory (DFT) with a semiempirical method reduces the computational cost for reaching a converged path that is an optimum under DFT by several fold. In conclusion, the approach also shows promise for free energy calculations when thermal noise can be controlled.
Authors:
 [1] ;  [2] ;  [3] ;  [4]
  1. Univ. of Chicago, IL (United States). Dept. of Chemistry; Univ. of Chicago, IL (United States). James Franck Inst.
  2. Univ. of Chicago, IL (United States). Dept. of Chemistry; Univ. of Chicago, IL (United States). James Franck Inst.; Univ. of Chicago, IL (United States). Inst. for Biophysical Dynamics; Univ. of Chicago, IL (United States). Computation Inst.; Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Univ. of Chicago, IL (United States). James Franck Inst.; Univ. of Chicago, IL (United States). Computation Inst.; Univ. of Chicago, IL (United States). Dept. of Statistics
  4. Univ. of Chicago, IL (United States). Dept. of Chemistry; Univ. of Chicago, IL (United States). James Franck Inst.; Univ. of Chicago, IL (United States). Inst. for Biophysical Dynamics; Univ. of Chicago, IL (United States). Computation Inst.
Publication Date:
Grant/Contract Number:
CHE-1136709; R01 GM109455-02; S10 RR029030-01; GM109455-02
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 10; Journal Issue: 12; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE; National Institutes of Health (NIH); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1261135

Kale, Seyit, Sode, Olaseni, Weare, Jonathan, and Dinner, Aaron R. Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol. United States: N. p., Web. doi:10.1021/ct500852y.
Kale, Seyit, Sode, Olaseni, Weare, Jonathan, & Dinner, Aaron R. Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol. United States. doi:10.1021/ct500852y.
Kale, Seyit, Sode, Olaseni, Weare, Jonathan, and Dinner, Aaron R. 2014. "Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol". United States. doi:10.1021/ct500852y. https://www.osti.gov/servlets/purl/1261135.
@article{osti_1261135,
title = {Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol},
author = {Kale, Seyit and Sode, Olaseni and Weare, Jonathan and Dinner, Aaron R.},
abstractNote = {Finding transition paths for chemical reactions can be computationally costly owing to the level of quantum-chemical theory needed for accuracy. Here, we show that a multilevel preconditioning scheme that was recently introduced (Tempkin et al. J. Chem. Phys. 2014, 140, 184114) can be used to accelerate quantum-chemical string calculations. We demonstrate the method by finding minimum-energy paths for two well-characterized reactions: tautomerization of malonaldehyde and Claissen rearrangement of chorismate to prephanate. For these reactions, we show that preconditioning density functional theory (DFT) with a semiempirical method reduces the computational cost for reaching a converged path that is an optimum under DFT by several fold. In conclusion, the approach also shows promise for free energy calculations when thermal noise can be controlled.},
doi = {10.1021/ct500852y},
journal = {Journal of Chemical Theory and Computation},
number = 12,
volume = 10,
place = {United States},
year = {2014},
month = {11}
}