Molecular-dynamics (MD) trajectories and high-level ab initio methods have been used to study the low-energy mechanism for D2O–H+(H2O)n reactions. At low collisional energies, MD simulations show that the collisional complexes are long-lived and undergo fast monomolecular isomerization, converting between different isomers within 50–500 ps. Such processes, primarily involving water-molecule shifts along a water chain, require the surmounting of very-low-energy barriers and present sizable non- Rice–Ramsperger–Kassel–Marcus (RRKM) effects, which are interpreted as a lack of randomization of the internal kinetic energy. Interestingly, the rate of water shifts was found to increase upon increasing the size of the cluster. Based on these findings, we propose to incorporate the following steps into the mechanism for low-energy isotopic scrambling these D2O–H+(H2O)n reactions: a) formation of the collisional complex [H+(H2O)nD2O]* in a vibro-rotational excited state; b) incorporation of the heavy-water molecule in the cluster core as HD2O+ by means of isomerization involving molecular shifts; c) displacement of solvation molecules from the first shell of HD2O+ inducing de-deuteration (shift of a D+ to a neighbor water molecule); d) reorganization of the clusters and/or expulsion of one of the isotopic variants of water (H2O, HDO or D2O) from the periphery of the complex.

Alternative low energy mechanisms for isotopic exchange in the gas phase reaction between D2O and H+(H2O)n (n=2-5)

MELLA, MASSIMO;
2006

Abstract

Molecular-dynamics (MD) trajectories and high-level ab initio methods have been used to study the low-energy mechanism for D2O–H+(H2O)n reactions. At low collisional energies, MD simulations show that the collisional complexes are long-lived and undergo fast monomolecular isomerization, converting between different isomers within 50–500 ps. Such processes, primarily involving water-molecule shifts along a water chain, require the surmounting of very-low-energy barriers and present sizable non- Rice–Ramsperger–Kassel–Marcus (RRKM) effects, which are interpreted as a lack of randomization of the internal kinetic energy. Interestingly, the rate of water shifts was found to increase upon increasing the size of the cluster. Based on these findings, we propose to incorporate the following steps into the mechanism for low-energy isotopic scrambling these D2O–H+(H2O)n reactions: a) formation of the collisional complex [H+(H2O)nD2O]* in a vibro-rotational excited state; b) incorporation of the heavy-water molecule in the cluster core as HD2O+ by means of isomerization involving molecular shifts; c) displacement of solvation molecules from the first shell of HD2O+ inducing de-deuteration (shift of a D+ to a neighbor water molecule); d) reorganization of the clusters and/or expulsion of one of the isotopic variants of water (H2O, HDO or D2O) from the periphery of the complex.
Mella, Massimo; Ponti, A.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11383/1736024
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