Aqueous Solution Chemistry of Ammonium Cation in the Auger Time Window

Abstract We report on chemical reactions triggered by core-level ionization of ammonium ( $${{\rm{NH}}}_{4}^{+}$$ NH 4 + ) cation in aqueous solution. Based on a combination of photoemission experiments from a liquid microjet and high-level ab initio simulations, we identified simultaneous single an...

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Autores principales:	Daniel Hollas, Marvin N. Pohl, Robert Seidel, Emad F. Aziz, Petr Slavíček, Bernd Winter
Formato:	article
Lenguaje:	EN
Publicado:	Nature Portfolio 2017
Materias:	Medicine R Science Q
Acceso en línea:	https://doaj.org/article/cde6ba4fadcc466b902ddae8c55846ee
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spelling	oai:doaj.org-article:cde6ba4fadcc466b902ddae8c55846ee2021-12-02T16:05:59ZAqueous Solution Chemistry of Ammonium Cation in the Auger Time Window10.1038/s41598-017-00756-x2045-2322https://doaj.org/article/cde6ba4fadcc466b902ddae8c55846ee2017-04-01T00:00:00Zhttps://doi.org/10.1038/s41598-017-00756-xhttps://doaj.org/toc/2045-2322Abstract We report on chemical reactions triggered by core-level ionization of ammonium ( $${{\rm{NH}}}_{4}^{+}$$ NH 4 + ) cation in aqueous solution. Based on a combination of photoemission experiments from a liquid microjet and high-level ab initio simulations, we identified simultaneous single and double proton transfer occurring on a very short timescale spanned by the Auger-decay lifetime. Molecular dynamics simulations indicate that the proton transfer to a neighboring water molecule leads to essentially complete formation of H3O+ (aq) and core-ionized ammonia $${({{\rm{NH}}}_{3}^{+})}^{\ast }$$ ( NH 3 + ) ⁎ (aq) within the ~7 fs lifetime of the nitrogen 1s core hole. A second proton transfer leads to a transient structure with the proton shared between the remaining NH2 moiety and another water molecule in the hydration shell. These ultrafast proton transfers are stimulated by very strong hydrogen bonds between the ammonium cation and water. Experimentally, the proton transfer dynamics is identified from an emerging signal at the high-kinetic energy side of the Auger-electron spectrum in analogy to observations made for other hydrogen-bonded aqueous solutions. The present study represents the most pronounced charge separation observed upon core ionization in liquids so far.Daniel HollasMarvin N. PohlRobert SeidelEmad F. AzizPetr SlavíčekBernd WinterNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 7, Iss 1, Pp 1-10 (2017)
institution	DOAJ
collection	DOAJ
language	EN
topic	Medicine R Science Q
spellingShingle	Medicine R Science Q Daniel Hollas Marvin N. Pohl Robert Seidel Emad F. Aziz Petr Slavíček Bernd Winter Aqueous Solution Chemistry of Ammonium Cation in the Auger Time Window
description	Abstract We report on chemical reactions triggered by core-level ionization of ammonium ( $${{\rm{NH}}}_{4}^{+}$$ NH 4 + ) cation in aqueous solution. Based on a combination of photoemission experiments from a liquid microjet and high-level ab initio simulations, we identified simultaneous single and double proton transfer occurring on a very short timescale spanned by the Auger-decay lifetime. Molecular dynamics simulations indicate that the proton transfer to a neighboring water molecule leads to essentially complete formation of H3O+ (aq) and core-ionized ammonia $${({{\rm{NH}}}_{3}^{+})}^{\ast }$$ ( NH 3 + ) ⁎ (aq) within the ~7 fs lifetime of the nitrogen 1s core hole. A second proton transfer leads to a transient structure with the proton shared between the remaining NH2 moiety and another water molecule in the hydration shell. These ultrafast proton transfers are stimulated by very strong hydrogen bonds between the ammonium cation and water. Experimentally, the proton transfer dynamics is identified from an emerging signal at the high-kinetic energy side of the Auger-electron spectrum in analogy to observations made for other hydrogen-bonded aqueous solutions. The present study represents the most pronounced charge separation observed upon core ionization in liquids so far.
format	article
author	Daniel Hollas Marvin N. Pohl Robert Seidel Emad F. Aziz Petr Slavíček Bernd Winter
author_facet	Daniel Hollas Marvin N. Pohl Robert Seidel Emad F. Aziz Petr Slavíček Bernd Winter
author_sort	Daniel Hollas
title	Aqueous Solution Chemistry of Ammonium Cation in the Auger Time Window
title_short	Aqueous Solution Chemistry of Ammonium Cation in the Auger Time Window
title_full	Aqueous Solution Chemistry of Ammonium Cation in the Auger Time Window
title_fullStr	Aqueous Solution Chemistry of Ammonium Cation in the Auger Time Window
title_full_unstemmed	Aqueous Solution Chemistry of Ammonium Cation in the Auger Time Window
title_sort	aqueous solution chemistry of ammonium cation in the auger time window
publisher	Nature Portfolio
publishDate	2017
url	https://doaj.org/article/cde6ba4fadcc466b902ddae8c55846ee
work_keys_str_mv	AT danielhollas aqueoussolutionchemistryofammoniumcationintheaugertimewindow AT marvinnpohl aqueoussolutionchemistryofammoniumcationintheaugertimewindow AT robertseidel aqueoussolutionchemistryofammoniumcationintheaugertimewindow AT emadfaziz aqueoussolutionchemistryofammoniumcationintheaugertimewindow AT petrslavicek aqueoussolutionchemistryofammoniumcationintheaugertimewindow AT berndwinter aqueoussolutionchemistryofammoniumcationintheaugertimewindow
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Aqueous Solution Chemistry of Ammonium Cation in the Auger Time Window

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