Density Functional Theory analysis of Dimethylphosphate hydrolysis: effect of solvation and nucleophile variation

Journal Article · Sat Jan 01 04:00:00 EST 2005 · Journal of Molecular Structure

DOI:https://doi.org/10.1016/j.theochem.2004.10.028· OSTI ID:932185

Imhof, Petra ^[1]; Fischer, S ^[1]; Kraemer, R ^[2]; Smith, Jeremy C ^[3]

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1. University of Heidelberg
2. Anorganisch-Chemisches Institut, Im Neuenheimer Feld 270
3. ORNL

We model the hydrolytic cleavage of dimethylphosphate by hydroxide ion and water in the gas phase and in implicit water using density functional theory. In all cases the rate-determining step is the nucleophilic attack. The barrier for this nucleophilic attack in vacuum is much larger for the hydroxide than for the neutral nucleophile. However, in water the barriers are similar. The rate-determining step in the attack by the neutral nucleophile involves the concerted transfer of a proton from the water molecule to the phosphate ion and the formation of the P-O bond.

• Research Organization: Oak Ridge National Laboratory (ORNL)
• Sponsoring Organization: ORNL Program Development
• DOE Contract Number: AC05-00OR22725
• OSTI ID: 932185
• Journal Information: Journal of Molecular Structure, Journal Name: Journal of Molecular Structure Journal Issue: 1-3 Vol. 713; ISSN JMOSB4; ISSN 0022-2860
• Country of Publication: United States
• Language: English

Related Subjects

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS
CLEAVAGE
FUNCTIONALS
HYDROLYSIS
HYDROXIDES
PHOSPHATES
PROTONS
SOLVATION
WATER