2015 | OriginalPaper | Buchkapitel
Unimolecular and hydrolysis channels for the detachment of water from microsolvated alkaline earth dication (Mg2+, Ca2+, Sr2+, Ba2+) clusters
verfasst von : Evangelos Miliordos, Sotiris S. Xantheas
Erschienen in: Thom H. Dunning, Jr.
Verlag: Springer Berlin Heidelberg
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We examine theoretically the three channels that are associated with the detachment of a single water molecule from the aqueous clusters of the alkaline earth dications, [M(H
2
O)
n
]
2+
, M = Mg, Ca, Sr, Ba,
n
≤ 6. These are the unimolecular water loss (M
2+
(H
2
O)
n
-1
+ H
2
O) and the two hydrolysis channels resulting the loss of hydronium ([MOH(H
2
O)
n
-2
]
+
+ H
3
O
+
) and Zundel ([MOH(H
2
O)
n
-3
]
+
+ H
3
O
+
(H
2
O)) cations. Minimum energy paths (MEPs) corresponding to those three channels were constructed at the Møller–Plesset second order perturbation (MP2) level of theory with basis sets of doubleand triple-ζ quality. We furthermore investigated the water and hydronium loss channels from the mono-hydroxide water clusters with up to four water molecules, [MOH (H
2
O)
n
]
+
, 1 ≤
n
≤ 4. Our results indicate the preference of the hydronium loss and possibly the Zundel-cation loss channels for the smallest size clusters, whereas the unimolecular water loss channel is preferred for the larger ones as well as the mono-hydroxide clusters. Although the charge separation (hydronium and Zundel-cation loss) channels produce more stable products when compared to the ones for the unimolecular water loss, they also require the surmounting of high-energy barriers, a fact that makes the experimental observation of fragments related to these hydrolysis channels difficult.