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Title: Multiple environment single system quantum mechanical/molecular mechanical (MESS-QM/MM) calculations. 1. Estimation of polarization energies

In combined quantum mechanical/molecular mechanical (QM/MM) free energy calculations, it is often advantageous to have a frozen geometry for the quantum mechanical (QM) region. For such multiple-environment single-system (MESS) cases, two schemes are proposed here for estimating the polarization energy: the first scheme, termed MESS-E, involves a Roothaan step extrapolation of the self-consistent field (SCF) energy; whereas the other scheme, termed MESS-H, employs a Newton–Raphson correction using an approximate inverse electronic Hessian of the QM region (which is constructed only once). Both schemes are extremely efficient, because the expensive Fock updates and SCF iterations in standard QM/MM calculations are completely avoided at each configuration. Here, they produce reasonably accurate QM/MM polarization energies: MESS-E can predict the polarization energy within 0.25 kcal/mol in terms of the mean signed error for two of our test cases, solvated methanol and solvated β-alanine, using the M06-2X or ωB97X-D functionals; MESS-H can reproduce the polarization energy within 0.2 kcal/mol for these two cases and for the oxyluciferin–luciferase complex, if the approximate inverse electronic Hessians are constructed with sufficient accuracy.
Authors:
 [1] ;  [2] ;  [1] ;  [3] ;  [4] ;  [1] ;  [5]
  1. National Institutes of Health, Rockville, MD (United States)
  2. National Institutes of Health, Rockville, MD (United States); East China Normal Univ., Shanghai (China); NYU-ECNU Center for Computational Chemistry at NYU Shanghai, Shanghai (China)
  3. Southern Methodist Univ., Dallas, TX (United States)
  4. Univ. of Utah, Salt Lake City, UT (United States)
  5. Q-Chem Inc., Pleasanton, CA (United States)
Publication Date:
Grant/Contract Number:
SC0011297
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 119; Journal Issue: 9; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Research Org:
Q-Chem Inc., Pleasanton, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1346161

Sodt, Alexander J., Mei, Ye, Konig, Gerhard, Tao, Peng, Steele, Ryan P., Brooks, Bernard R., and Shao, Yihan. Multiple environment single system quantum mechanical/molecular mechanical (MESS-QM/MM) calculations. 1. Estimation of polarization energies. United States: N. p., Web. doi:10.1021/jp5072296.
Sodt, Alexander J., Mei, Ye, Konig, Gerhard, Tao, Peng, Steele, Ryan P., Brooks, Bernard R., & Shao, Yihan. Multiple environment single system quantum mechanical/molecular mechanical (MESS-QM/MM) calculations. 1. Estimation of polarization energies. United States. doi:10.1021/jp5072296.
Sodt, Alexander J., Mei, Ye, Konig, Gerhard, Tao, Peng, Steele, Ryan P., Brooks, Bernard R., and Shao, Yihan. 2014. "Multiple environment single system quantum mechanical/molecular mechanical (MESS-QM/MM) calculations. 1. Estimation of polarization energies". United States. doi:10.1021/jp5072296. https://www.osti.gov/servlets/purl/1346161.
@article{osti_1346161,
title = {Multiple environment single system quantum mechanical/molecular mechanical (MESS-QM/MM) calculations. 1. Estimation of polarization energies},
author = {Sodt, Alexander J. and Mei, Ye and Konig, Gerhard and Tao, Peng and Steele, Ryan P. and Brooks, Bernard R. and Shao, Yihan},
abstractNote = {In combined quantum mechanical/molecular mechanical (QM/MM) free energy calculations, it is often advantageous to have a frozen geometry for the quantum mechanical (QM) region. For such multiple-environment single-system (MESS) cases, two schemes are proposed here for estimating the polarization energy: the first scheme, termed MESS-E, involves a Roothaan step extrapolation of the self-consistent field (SCF) energy; whereas the other scheme, termed MESS-H, employs a Newton–Raphson correction using an approximate inverse electronic Hessian of the QM region (which is constructed only once). Both schemes are extremely efficient, because the expensive Fock updates and SCF iterations in standard QM/MM calculations are completely avoided at each configuration. Here, they produce reasonably accurate QM/MM polarization energies: MESS-E can predict the polarization energy within 0.25 kcal/mol in terms of the mean signed error for two of our test cases, solvated methanol and solvated β-alanine, using the M06-2X or ωB97X-D functionals; MESS-H can reproduce the polarization energy within 0.2 kcal/mol for these two cases and for the oxyluciferin–luciferase complex, if the approximate inverse electronic Hessians are constructed with sufficient accuracy.},
doi = {10.1021/jp5072296},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 9,
volume = 119,
place = {United States},
year = {2014},
month = {10}
}