CH ₂ Cl ₂ + OH ^- Reaction in Aqueous Solution: A Combined Quantum Mechanical and Molecular Mechanics Study

Journal Article · Thu Mar 03 04:00:00 EST 2011 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/jp109287r· OSTI ID:1008232

Wang, Dunyou; Valiev, Marat; Garrett, Bruce C.

The CH₂Cl₂ + OH^- reaction in aqueous solution was investigated using combined quantum mechanical and molecular mechanics approach. We present analysis of the reactant, transition, and product state structures, and calculate the free energy reaction profile through the CCSD(T) level of the theory for the reactive region. Our results show that the aqueous environment has a significant impact on the reaction process raising the reaction barrier by ~17 kcal/mol and the reaction energy by ~20 kcal/mol. While solvation effects play a predominant role, we also find sizable contributions from solvent-induced polarization effects.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1008232
• Report Number(s): PNNL-SA-75398; 34900; KC0301020
• Journal Information: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 8 Vol. 115; ISSN 1089-5639
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
AQUEOUS SOLUTIONS
Environmental Molecular Sciences Laboratory
FREE ENERGY
POLARIZATION
SOLVATION
aqueous
quantum mechanical and molecular mechanics
solvation