Acid Solvation Versus Dissociation at "stardust Conditions": Reaction Sequence Matters

Overview

Journal Sci Adv

Specialties Biology
Science

Date 2019 Jun 13

PMID 31187059

Citations 5

Authors

Devendra Mani

Ricardo Perez de Tudela

Raffael Schwan

Nitish Pal

Saskia Korning

Harald Forbert

Britta Redlich

A F G van der Meer

Gerhard Schwaab

Dominik Marx

Martina Havenith

Affiliations

Soon will be listed here.

Abstract

Chemical reactions at ultralow temperatures are of fundamental importance to primordial molecular evolution as it occurs on icy mantles of dust nanoparticles or on ultracold water clusters in dense interstellar clouds. As we show, studying reactions in a stepwise manner in ultracold helium nanodroplets by mass-selective infrared (IR) spectroscopy provides an avenue to mimic these "stardust conditions" in the laboratory. In our joint experimental/theoretical study, in which we successively add HO molecules to HCl, we disclose a unique IR fingerprint at 1337 cm that heralds hydronium (HO) formation and, thus, acid dissociation generating solvated protons. In stark contrast, no reaction is observed when reversing the sequence by allowing HCl to interact with preformed small embryonic ice-like clusters. Our ab initio simulations demonstrate that not only reaction stoichiometry but also the reaction sequence needs to be explicitly considered to rationalize ultracold chemistry.

Citing Articles

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Unveiling Zwitterionization of Glycine in the Microhydration Limit.

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Slowing Down of the Molecular Reorientation of Water in Concentrated Alkaline Solutions.

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References

Nauta , Miller . Formation of cyclic water hexamer in liquid helium: the smallest piece of Ice. Science. 2000; 287(5451):293-5. DOI: 10.1126/science.287.5451.293. View

Bolton K, Pettersson J . Ice-catalyzed ionization of hydrochloric acid. J Am Chem Soc. 2001; 123(30):7360-3. DOI: 10.1021/ja010096c. View

Devlin J, Uras N, Sadlej J, Buch V . Discrete stages in the solvation and ionization of hydrogen chloride adsorbed on ice particles. Nature. 2002; 417(6886):269-71. DOI: 10.1038/417269a. View

Asmis K, Pivonka N, Santambrogio G, Brummer M, Kaposta C, Neumark D . Gas-phase infrared spectrum of the protonated water dimer. Science. 2003; 299(5611):1375-7. DOI: 10.1126/science.1081634. View

Rini M, Magnes B, Pines E, Nibbering E . Real-time observation of bimodal proton transfer in acid-base pairs in water. Science. 2003; 301(5631):349-52. DOI: 10.1126/science.1085762. View

Hornekaer L, Baurichter A, Petrunin V, Field D, Luntz A . Importance of surface morphology in interstellar H2 formation. Science. 2003; 302(5652):1943-6. DOI: 10.1126/science.1090820. View

Miyazaki M, Fujii A, Ebata T, Mikami N . Infrared spectroscopic evidence for protonated water clusters forming nanoscale cages. Science. 2004; 304(5674):1134-7. DOI: 10.1126/science.1096037. View

Shin J, Hammer N, Diken E, Johnson M, Walters R, Jaeger T . Infrared signature of structures associated with the H+(H2O)n (n = 6 to 27) clusters. Science. 2004; 304(5674):1137-40. DOI: 10.1126/science.1096466. View

Headrick J, Diken E, Walters R, Hammer N, Christie R, Cui J . Spectral signatures of hydrated proton vibrations in water clusters. Science. 2005; 308(5729):1765-9. DOI: 10.1126/science.1113094. View

10.

Woutersen S, Bakker H . Ultrafast vibrational and structural dynamics of the proton in liquid water. Phys Rev Lett. 2006; 96(13):138305. DOI: 10.1103/PhysRevLett.96.138305. View

11.

Parent P, Laffon C . Adsorption of HCl on the water ice surface studied by X-ray absorption spectroscopy. J Phys Chem B. 2006; 109(4):1547-53. DOI: 10.1021/jp040518f. View

12.

Marx D . Proton transfer 200 years after von Grotthuss: insights from ab initio simulations. Chemphyschem. 2006; 7(9):1848-70. DOI: 10.1002/cphc.200600128. View

13.

Molina M, Tso T, Molina L, Wang F . Antarctic stratospheric chemistry of chlorine nitrate, hydrogen chloride, and ice: release of active chlorine. Science. 1987; 238(4831):1253-7. DOI: 10.1126/science.238.4831.1253. View

14.

Oncak M, Slavicek P, Poterya V, Farnik M, Buck U . Emergence of charge-transfer-to-solvent band in the absorption spectra of hydrogen halides on ice nanoparticles: spectroscopic evidence for acidic dissociation. J Phys Chem A. 2008; 112(24):5344-53. DOI: 10.1021/jp8012305. View

15.

Gutberlet A, Schwaab G, Birer O, Masia M, Kaczmarek A, Forbert H . Aggregation-induced dissociation of HCl(H2O)4 below 1 K: the smallest droplet of acid. Science. 2009; 324(5934):1545-8. DOI: 10.1126/science.1171753. View

16.

Forbert H, Masia M, Kaczmarek-Kedziera A, Nair N, Marx D . Aggregation-induced chemical reactions: acid dissociation in growing water clusters. J Am Chem Soc. 2011; 133(11):4062-72. DOI: 10.1021/ja1099209. View

17.

Parent P, Lasne J, Marcotte G, Laffon C . HCl adsorption on ice at low temperature: a combined X-ray absorption, photoemission and infrared study. Phys Chem Chem Phys. 2011; 13(15):7142-8. DOI: 10.1039/c0cp02864a. View

18.

Hogerheijde M, Bergin E, Brinch C, Cleeves L, Fogel J, Blake G . Detection of the water reservoir in a forming planetary system. Science. 2011; 334(6054):338-40. DOI: 10.1126/science.1208931. View

19.

Devlin J, Kang H . Comment on "HCl adsorption on ice at low temperature: a combined X-ray absorption, photoemission and infrared study" by P. Parent, J. Lasne, G. Marcotte and C. Laffon, Phys. Chem. Chem. Phys., 2011, 13, 7142. Phys Chem Chem Phys. 2011; 14(2):1048-9. DOI: 10.1039/c1cp22007a. View

20.

Walewski L, Forbert H, Marx D . Revealing the subtle interplay of thermal and quantum fluctuation effects on contact ion pairing in microsolvated HCl. Chemphyschem. 2012; 14(4):817-26. DOI: 10.1002/cphc.201200695. View