Thermodynamic Study of Hydrolysis Reactions in Aqueous Solution from Ab Initio Potential and Molecular Dynamics Simulations

被引：1

作者：

Tolosa, S. ^{[1
]}

Hidalgo, A. ^{[1
]}

Sanson, J. A. ^{[1
]}

机构：

[1] Univ Extremadura, Dept Ingn Quim & Quim Fis, E-06071 Badajoz, Spain

来源：

JOURNAL OF CHEMISTRY | 2013年 / 2013卷

关键词：

GAUSSIAN-TYPE BASIS; FREE-ENERGY CHANGE; ALKALINE-HYDROLYSIS; ESTER HYDROLYSIS; ACID IONIZATION; ORBITAL METHODS; WATER; MECHANISM; FORMAMIDE; DECOMPOSITION;

D O I：

10.1155/2013/265958

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A procedure for the theoretical study of chemical reactions in solution by means of molecular dynamics simulations of aqueous solution at infinite dilution is described using ab initio solute-solvent potentials and TIP3P water model to describe the interactions. The procedure is applied to the study of neutral hydrolysis of various molecules (HCONH2, HNCO, HCNHNH2, and HCOOCH3) via concerted and water-assisted mechanisms. We used the solvent as a reaction coordinate and the free energy curves for the calculation of the properties related with the reaction mechanism, namely, reaction and activation energies.

引用

页数：8

共 60 条

[1] STUDIES IN MOLECULAR DYNAMICS .1. GENERAL METHOD [J].

ALDER, BJ ;

WAINWRIGHT, TE .

JOURNAL OF CHEMICAL PHYSICS, 1959, 31 (02) :459-466

[2] Ab initio study of the decomposition of formamidine [J].

Almatarneh, MH ;

Flinn, CG ;

Poirier, RA .

CANADIAN JOURNAL OF CHEMISTRY, 2005, 83 (12) :2082-2090

[3]

Almetindo GI, 2007, J BRAZIL CHEM SOC, V18, P696

[4] Molecular mechanism of HF acid ionization in water: An electronic structure - Monte Carlo study [J].

Ando, K ;

Hynes, JT .

JOURNAL OF PHYSICAL CHEMISTRY A, 1999, 103 (49) :10398-10408

[5] Molecular mechanism of HCl acid ionization in water: Ab initio potential energy surfaces and Monte Carlo simulations [J].

Ando, K ;

Hynes, JT .

JOURNAL OF PHYSICAL CHEMISTRY B, 1997, 101 (49) :10464-10478

[6] AN ABINITIO STUDY OF THE UNIMOLECULAR DECOMPOSITION MECHANISM OF FORMAMIDINE - 4-31G CHARACTERIZATION OF POTENTIAL-ENERGY HYPERSURFACE [J].

ANDRES, J ;

KRECHL, J ;

CARDA, M ;

SILLA, E .

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1991, 40 (01) :127-137

[7]

ANDRES J, 1992, J MOL STRUC-THEOCHEM, V86, P465

[8] The hydrolysis mechanism of formamide revisited: Comparison between ab initio, semiempirical and DFT results [J].

Antonczak, S ;

RuizLopez, M ;

Rivail, JL .

JOURNAL OF MOLECULAR MODELING, 1997, 3 (10) :434-442

[9] Theoretical-experimental study of the solvation enthalpy of acetone in dilute aqueous solution [J].

Arroyo, ST ;

Martín, JAS ;

García, AH .

CHEMICAL PHYSICS, 2005, 315 (1-2) :76-80

[10] Thermodynamic and dielectric properties of aqueous solutions using ESIE charges to describe small solutes [J].

Arroyo, ST ;

Martín, JAS ;

García, AH .

CHEMICAL PHYSICS, 2003, 293 (02) :193-202

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