+ Site Statistics
+ Search Articles
+ PDF Full Text Service
How our service works
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ Translate
+ Recently Requested

Hybrid Quantum Mechanics/Molecular Mechanics Solvation Scheme for Computing Free Energies of Reactions at Metal-Water Interfaces



Hybrid Quantum Mechanics/Molecular Mechanics Solvation Scheme for Computing Free Energies of Reactions at Metal-Water Interfaces



Journal of Chemical Theory and Computation 10(8): 3354-3368



We report the development of a quantum mechanics/molecular mechanics free energy perturbation (QM/MM-FEP) method for modeling chemical reactions at metal-water interfaces. This novel solvation scheme combines planewave density function theory (DFT), periodic electrostatic embedded cluster method (PEECM) calculations using Gaussian-type orbitals, and classical molecular dynamics (MD) simulations to obtain a free energy description of a complex metal-water system. We derive a potential of mean force (PMF) of the reaction system within the QM/MM framework. A fixed-size, finite ensemble of MM conformations is used to permit precise evaluation of the PMF of QM coordinates and its gradient defined within this ensemble. Local conformations of adsorbed reaction moieties are optimized using sequential MD-sampling and QM-optimization steps. An approximate reaction coordinate is constructed using a number of interpolated states and the free energy difference between adjacent states is calculated using the QM/MM-FEP method. By avoiding on-the-fly QM calculations and by circumventing the challenges associated with statistical averaging during MD sampling, a computational speedup of multiple orders of magnitude is realized. The method is systematically validated against the results of ab initio QM calculations and demonstrated for C-C cleavage in double-dehydrogenated ethylene glycol on a Pt (111) model surface.

Please choose payment method:






(PDF emailed within 0-6 h: $19.90)

Accession: 058020583

Download citation: RISBibTeXText

PMID: 26588304

DOI: 10.1021/ct500211w


Related references

Free energies of chemical reactions in solution and in enzymes with ab initio quantum mechanics/molecular mechanics methods. Annual Review of Physical Chemistry 59: 573-601, 2008

Combined quantum mechanics/molecular mechanics (QM/MM) simulations for protein-ligand complexes: free energies of binding of water molecules in influenza neuraminidase. Journal of Physical Chemistry. B 119(3): 997, 2015

Solvation Free Energy Calculations with Quantum Mechanics/Molecular Mechanics and Machine Learning Models. Journal of Physical Chemistry. B 123(4): 901-908, 2019

An efficient method for the calculation of quantum mechanics/molecular mechanics free energies. Journal of Chemical Physics 128(1): 014109, 2008

Protein/ligand binding free energies calculated with quantum mechanics/molecular mechanics. Journal of Physical Chemistry. B 109(20): 10474-10483, 2005

Photostability Mechanisms in Human γB-Crystallin: Role of the Tyrosine Corner Unveiled by Quantum Mechanics and Hybrid Quantum Mechanics/Molecular Mechanics Methodologies. Journal of Chemical Theory and Computation 8(4): 1351-1359, 2012

Solvation free energies of amino acid side chain analogs for common molecular mechanics water models. Journal of Chemical Physics 122(13): 134508, 2005

Quantum mechanics/molecular mechanics modeling of photoelectron spectra: the carbon 1s core-electron binding energies of ethanol-water solutions. Journal of Physical Chemistry. B 118(46): 13217-13225, 2014

Mechanistic insights into Mg2+-independent prenylation by CloQ from classical molecular mechanics and hybrid quantum mechanics/molecular mechanics molecular dynamics simulations. Biochemistry 53(30): 5034-5041, 2014

Ab initio quantum mechanics-based free energy perturbation method for calculating relative solvation free energies. Journal of Computational Chemistry 28(2): 491-494, 2007

Development of a quantum mechanics-based free-energy perturbation method: use in the calculation of relative solvation free energies. Journal of the American Chemical Society 126(20): 6224-6225, 2004

Calculations of Solvation Free Energy through Energy Reweighting from Molecular Mechanics to Quantum Mechanics. Journal of Chemical Theory and Computation 12(2): 499-511, 2016

Vibrational spectrum at a water surface: a hybrid quantum mechanics/molecular mechanics molecular dynamics approach. Journal of Physics. Condensed Matter 24(12): 124107, 2012

Hybrid quantum mechanics/molecular mechanics-based molecular dynamics simulation of acid-catalyzed dehydration of polyols in liquid water. Journal of Physical Chemistry. a 115(32): 8816-8821, 2011

Cation solvation with quantum chemical effects modeled by a size-consistent multi-partitioning quantum mechanics/molecular mechanics method. Physical Chemistry Chemical Physics 19(27): 17985-17997, 2017