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Science 19 June 2009:
Vol. 324. no. 5934, pp. 1545 - 1548
DOI: 10.1126/science.1171753
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Reports

Aggregation-Induced Dissociation of HCl(H2O)4 Below 1 K: The Smallest Droplet of Acid

Anna Gutberlet,1 Gerhard Schwaab,1 Özgür Birer,1,* Marco Masia,2,{dagger} Anna Kaczmarek,2,{ddagger} Harald Forbert,2 Martina Havenith,1,§ Dominik Marx2

Acid dissociation and the subsequent solvation of the charged fragments at ultracold temperatures in nanoenvironments, as distinct from ambient bulk water, are relevant to atmospheric and interstellar chemistry but remain poorly understood. Here we report the experimental observation of a nanoscopic aqueous droplet of acid formed within a superfluid helium cluster at 0.37 kelvin. High-resolution mass-selective infrared laser spectroscopy reveals that successive aggregation of the acid HCl with water molecules, HCl(H2O)n, readily results in the formation of hydronium at n = 4. Accompanying ab initio simulations show that undissociated clusters assemble by stepwise water molecule addition in electrostatic steering arrangements up to n = 3. Adding a fourth water molecule to the ringlike undissociated HCl(H2O)3 then spontaneously yields the compact dissociated H3O+(H2O)3Cl– ion pair. This aggregation mechanism bypasses deep local energy minima on the n = 4 potential energy surface and offers a general paradigm for reactivity at ultracold temperatures.

1 Lehrstuhl für Physikalische Chemie II, Ruhr-Universität Bochum, 44780 Bochum, Germany.
2 Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany.

* Present address: Department of Chemistry, Koc University, Rumelifeneri Yolu Sariyer, 34450 Istanbul, Turkey.

{dagger} Present address: Dipartimento di Chimica, Università degli Studi di Sassari, CNR-INFM SLACS and INSTM, Via Vienna 2, 07100 Sassari, Italy.

{ddagger} Present address: Faculty of Chemistry, Nicolaus Copernicus University, Gagarina 7, 87-100 Torun, Poland.

§ To whom correspondence should be addressed. E-mail: martina.havenith{at}rub.de

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THIS ARTICLE HAS BEEN CITED BY OTHER ARTICLES:
Squeezing the Water Out of HCl(aq).
T. S. Zwier (2009)
Science 324, 1522-1523
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