TY - JOUR
T1 - Reaction free energies in organic solvents
T2 - Comparing different quantum mechanical methods
AU - Konstantinov, Ivan A.
AU - Broadbelt, Linda J.
N1 - Funding Information:
Funding through the Institute for Catalysis in Energy Processes (ICEP) at Northwestern University which is sponsored by DOE is acknowledged. Computational resources used for this study were available through NERSC.
PY - 2010/12
Y1 - 2010/12
N2 - A variety of quantum mechanical (QM) methods, basis sets and solute cavity descriptions using the conductor-like polarisable continuum model for the modelling of reaction free energies in solution have been evaluated and compared. In order to test the performance of each QM level of theory and cavity model, five common types of organic reactions in different solvents have been considered. The study shows that the hybrid metageneralised-gradient approximation M05-2X functional, in conjunction with the MG3S basis set and UA0 or universal force field cavities, produces results in the best overall agreement with experimental data. In addition, within the UA0 formalism, explicit cavities should be built on the hydrogen atoms that undergo transformation during chemical reaction.
AB - A variety of quantum mechanical (QM) methods, basis sets and solute cavity descriptions using the conductor-like polarisable continuum model for the modelling of reaction free energies in solution have been evaluated and compared. In order to test the performance of each QM level of theory and cavity model, five common types of organic reactions in different solvents have been considered. The study shows that the hybrid metageneralised-gradient approximation M05-2X functional, in conjunction with the MG3S basis set and UA0 or universal force field cavities, produces results in the best overall agreement with experimental data. In addition, within the UA0 formalism, explicit cavities should be built on the hydrogen atoms that undergo transformation during chemical reaction.
KW - ab initio
KW - conductor-like polarisable continuum model
KW - density functional theory
KW - organic solvents
KW - reaction free energies
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U2 - 10.1080/08927020903483288
DO - 10.1080/08927020903483288
M3 - Article
AN - SCOPUS:84962449866
SN - 0892-7022
VL - 36
SP - 1197
EP - 1207
JO - Molecular Simulation
JF - Molecular Simulation
IS - 15
ER -