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Efficient Computation of Free Energy Surfaces of Diels–Alder Reactions in Explicit Solvent at Ab Initio QM/MM Level

Journal Article · · Molecules
 [1];  [2];  [2];  [3];  [4];  [4];  [5]
  1. East China Normal Univ., Shanghai (China). State Key Lab. of Precision Spectroscopy, School of Physics and Materials Science; DOE/OSTI
  2. East China Normal Univ., Shanghai (China). State Key Lab. of Precision Spectroscopy, School of Physics and Materials Science
  3. Univ. of Oklahoma, Norman, OK (United States)
  4. East China Normal Univ., Shanghai (China). Computer Center, School of Computer Science and Software Engineering
  5. East China Normal Univ., Shanghai (China). State Key Lab. of Precision Spectroscopy, School of Physics and Materials Science; Univ. of Oklahoma, Norman, OK (United States); NYU Shanghai, Shanghai (China). NYU-ECNU Center for Computational Chemistry
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For Diels–Alder (DA) reactions in solution, an accurate and converged free energy (FE) surface at ab initio (ai) quantum mechanical/molecular mechanical (QM/MM) level is imperative for the understanding of reaction mechanism. However, this computation is still far too expensive. In a previous work, we proposed a new method termed MBAR+wTP, with which the computation of the ai FE profile can be accelerated by several orders of magnitude via a three-step procedure: (I) an umbrella sampling (US) using a semi-empirical (SE) QM/MM Hamiltonian is performed; (II) the FE profile is generated using the Multistate Bennett Acceptance Ratio (MBAR) analysis; and (III) a weighted Thermodynamic Perturbation (wTP) from the SE Hamiltonian to the ai Hamiltonian is performed to obtain the ai QM/MM FE profile using weight factors from the MBAR analysis. In this work, this method is extended to the calculations of two-dimensional FE surfaces of two Diels–Alder reactions of cyclopentadiene with either acrylonitrile or 1-4-naphthoquinone at ai QM/MM level. The accurate activation free energies at the ai QM/MM level, which are much closer to the experimental measurements than those calculated by other methods, indicate that this MBAR+wTP method can be applied in the studies of complex reactions in condensed phase with much-enhanced efficiency.
Research Organization:
Q-Chem, Inc., Pleasanton, CA (United States)
Sponsoring Organization:
National Natural Science Foundation of China (NNSFC); USDOE Office of Science (SC)
Grant/Contract Number:
SC0011297
OSTI ID:
1611615
Journal Information:
Molecules, Journal Name: Molecules Journal Issue: 10 Vol. 23; ISSN MOLEFW; ISSN 1420-3049
Publisher:
MDPICopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Biochemistry & Molecular Biology
Chemistry
Diels–Alder reaction
ab initio
free energy surface
reference-potential method
umbrella sampling