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 |
| Publication status | Published - Jan 8 2004 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
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Formamide hydrolysis investigated by multiple-steering ab initio molecular dynamics. / Cascella, Michele; Raugei, Simone; Carloni, Paoli.
In: Journal of Physical Chemistry B, Vol. 108, No. 1, 08.01.2004, p. 369-375.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Formamide hydrolysis investigated by multiple-steering ab initio molecular dynamics
AU - Cascella, Michele
AU - Raugei, Simone
AU - Carloni, Paoli
PY - 2004/1/8
Y1 - 2004/1/8
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.
UR - http://www.scopus.com/inward/record.url?scp=1642439051&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=1642439051&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:1642439051
VL - 108
SP - 369
EP - 375
JO - Journal of Physical Chemistry B Materials
JF - Journal of Physical Chemistry B Materials
SN - 1520-6106
IS - 1
ER -