title: Theoretical Modeling on the Reaction Mechanism of p-Nitrophenylmethylphosphate Alkaline Hydrolysis and its Kinetic Isotope Effects.
abstract: We have studied the alkaline hydrolysis of p-nitrophenylmethylphosphate (p-NPmP) in aqueous solution by means of polarizable continuum models and by hybrid quantum-mechanical/molecular-mechanical (QM/MM) methods. The theoretical predictions of kinetic isotope effects (KIEs) are in very good agreement with the experimental data, confirming a concerted asynchronous molecular mechanism. In addition, comparison of high level DFT theory with semiempirical AM1/d Hamiltonian has allowed checking the reliability of the later to be used in modeling very large molecular models containing phosphorus atoms.
authors.affiliation: Departamento de Química Física, Universidad de Valencia, 46100 Burjassot, Spain, Department of Chemistry, University of Bath, Bath BA2 7AY, United Kingdom, and Departament de Química Física i Analítica, Universitat Jaume I, 12071 Castellón, Spain.
authors.forename: Violeta
authors.initials: V
authors.lastname: López-Canut
authors.affiliation: Departamento de Química Física, Universidad de Valencia, 46100 Burjassot, Spain, Department of Chemistry, University of Bath, Bath BA2 7AY, United Kingdom, and Departament de Química Física i Analítica, Universitat Jaume I, 12071 Castellón, Spain.
authors.forename: Javier
authors.initials: J
authors.lastname: Ruiz-Pernía
authors.affiliation: Departamento de Química Física, Universidad de Valencia, 46100 Burjassot, Spain, Department of Chemistry, University of Bath, Bath BA2 7AY, United Kingdom, and Departament de Química Física i Analítica, Universitat Jaume I, 12071 Castellón, Spain.
authors.forename: Iñaki
authors.initials: I
authors.lastname: Tuñón
authors.affiliation: Departamento de Química Física, Universidad de Valencia, 46100 Burjassot, Spain, Department of Chemistry, University of Bath, Bath BA2 7AY, United Kingdom, and Departament de Química Física i Analítica, Universitat Jaume I, 12071 Castellón, Spain.
authors.forename: Silvia
authors.initials: S
authors.lastname: Ferrer
authors.affiliation: Departamento de Química Física, Universidad de Valencia, 46100 Burjassot, Spain, Department of Chemistry, University of Bath, Bath BA2 7AY, United Kingdom, and Departament de Química Física i Analítica, Universitat Jaume I, 12071 Castellón, Spain.
authors.forename: Vicent
authors.initials: V
authors.lastname: Moliner