Formamide hydrolysis investigated by multiple-steering ab initio molecular dynamics

Michele Cascella; Simone Raugei; Paoli Carloni

doi:10.1021/jp035458c

Formamide hydrolysis investigated by multiple-steering ab initio molecular dynamics

Michele Cascella, Simone Raugei, Paoli Carloni

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

48 Citations (Scopus)

Abstract

The first step of formamide hydrolysis in aqueous solution has been studied coupling ab initio molecular dynamics to the multiple-steering molecular dynamics approach. We have investigated the reaction at both neutral (water addition) and alkaline (hydroxyl ion addition) pH. The activation barrier of the water-addition reaction (44 kcal mol^-1) is much larger than that of the reaction catalyzed at alkaline pH (15 kcal mol^-1). The solvation shell structure of the hydroxyl anion plays an important role in the dynamical and energetic properties. In particular, the free-energy profile for the hydroxyl ion addition is completely solvent induced, and its transition state properties can be essentially related to the dynamics of the hydration shell of the hydroxyl ion.

Original language	English
Pages (from-to)	369-375
Number of pages	7
Journal	Journal of Physical Chemistry B
Volume	108
Issue number	1
DOIs	https://doi.org/10.1021/jp035458c
Publication status	Published - Jan 8 2004

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Surfaces, Coatings and Films
Materials Chemistry

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N2 - The first step of formamide hydrolysis in aqueous solution has been studied coupling ab initio molecular dynamics to the multiple-steering molecular dynamics approach. We have investigated the reaction at both neutral (water addition) and alkaline (hydroxyl ion addition) pH. The activation barrier of the water-addition reaction (44 kcal mol-1) is much larger than that of the reaction catalyzed at alkaline pH (15 kcal mol-1). The solvation shell structure of the hydroxyl anion plays an important role in the dynamical and energetic properties. In particular, the free-energy profile for the hydroxyl ion addition is completely solvent induced, and its transition state properties can be essentially related to the dynamics of the hydration shell of the hydroxyl ion.

AB - The first step of formamide hydrolysis in aqueous solution has been studied coupling ab initio molecular dynamics to the multiple-steering molecular dynamics approach. We have investigated the reaction at both neutral (water addition) and alkaline (hydroxyl ion addition) pH. The activation barrier of the water-addition reaction (44 kcal mol-1) is much larger than that of the reaction catalyzed at alkaline pH (15 kcal mol-1). The solvation shell structure of the hydroxyl anion plays an important role in the dynamical and energetic properties. In particular, the free-energy profile for the hydroxyl ion addition is completely solvent induced, and its transition state properties can be essentially related to the dynamics of the hydration shell of the hydroxyl ion.

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