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Charge Dependence of Solvent-Mediated Intermolecular Coster-Kronig Decay Dynamics of Aqueous Ions
MAX-lab, Lund UniVersity.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Fysiska sektionen, Institutionen för fysik och astronomi, Yt- och gränsskiktsvetenskap.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Fysiska sektionen, Institutionen för fysik och astronomi, Yt- och gränsskiktsvetenskap.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Fysiska sektionen, Institutionen för fysik och astronomi.
Vise andre og tillknytning
2010 (engelsk)Inngår i: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 114, nr 51, s. 17057-17061Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

The 2s and 2p photoelectron spectra have been measured for Na+, Mg2+, and Al3+ ions in aqueous solution.In all cases, the 2s lines are significantly broader than the 2p features, which is attributed to a shorter lifetimeof the respective 2s hole. Since intraionic Coster-Kronig decay channels from the (2s)-1 state are closed forfree Na+, Mg2+, and Al3+ ions, this is evidence for an intermolecular Coster-Kronig-like process, reminiscentof intermolecular Coulombic decay (ICD), involving neighboring water solvent molecules. The observed 2s Lorentzian line widths correspond to lifetimes of the (2s)-1 state of 3.1, 1.5, and 0.98 fs for the solvated Na,Mg, and Al ions, respectively.

sted, utgiver, år, opplag, sider
2010. Vol. 114, nr 51, s. 17057-17061
HSV kategori
Forskningsprogram
Fysik med inriktning mot atom- molekyl- och kondenserande materiens fysik
Identifikatorer
URN: urn:nbn:se:uu:diva-138741DOI: 10.1021/jp108956vISI: 000285560100006OAI: oai:DiVA.org:uu-138741DiVA, id: diva2:379723
Tilgjengelig fra: 2010-12-19 Laget: 2010-12-19 Sist oppdatert: 2017-12-11bibliografisk kontrollert
Inngår i avhandling
1. Solvent–Solute Interaction: Studied by Synchrotron Radiation Based Photo and Auger Electron Spectroscopies
Åpne denne publikasjonen i ny fane eller vindu >>Solvent–Solute Interaction: Studied by Synchrotron Radiation Based Photo and Auger Electron Spectroscopies
2011 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
Abstract [en]

Aqueous solutions were studied using photoelectron and Auger spectroscopy, based on synchrotron radiation and a liquid micro-jet setup.

By varying the photon energy in photoelectron spectra, we depth profiled an aqueous tetrabutylammonium iodide (TBAI) solution. Assuming uniform angular emission from the core levels, we found that the TBA+ ions were oriented at the surface with the hydrophobic butyl arms sticking into the liquid.

We investigated the association between ions and their neighbors in aqueous solutions by studying the electronic decay after core ionization. The (2p)−1 decay of solvated K+ and Ca2+ ions was studied. The main features in the investigated decay spectra corresponded to two-hole final states localized on the ions. The spectra also showed additional features, related to delocalized two-hole final states with vacancies on a cation and a neighboring water molecule. These two processes compete, and by comparing relative intensities and using the known rate for the localized decay, we determined the time-scale for the delocalized process for the two ions. We compared to delocalized electronic decay processes in Na+, Mg2+, and Al3+, and found that they were slower in K+ and Ca2+, due to different internal decay mechanisms of the ions, as well as external differences in the ion-solute distances and interactions.

In the O 1s Auger spectra of aqueous metal halide solutions, we observed features related to delocalized two-hole final states with vacancies on a water molecule and a neighboring solvated anion. The relative intensity of these feature indicated that the strength of the interaction between the halide ions and water correlated with ionic size.

The delocalized decay was also used to investigate contact ion pair formation in high concentrated potassium halide solutions, but no concrete evidence of contact ion pairs was observed.

sted, utgiver, år, opplag, sider
Uppsala: Acta Universitatis Upsaliensis, 2011. s. 73
Serie
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 796
Emneord
Interatomic Coulombic Decay, ICD, Auger electron spectroscopy, AES, X-ray photoelectron spectroscopy, XPS, Ultra-violet spectroscopy, UPS, localized, delocalized, double ionization potential, DIP, two hole, final states, Water, H2O, Potassium chloride, KCl, Calcium chloride, CaCl2, Ammonium, NH4, Core hole, clock, lifetime, solvated, ion, alkali, halide, Coster Kronig, MAX-lab, BESSY
HSV kategori
Forskningsprogram
Fysik med inriktning mot atom- molekyl- och kondenserande materiens fysik
Identifikatorer
urn:nbn:se:uu:diva-138749 (URN)978-91-554-7980-0 (ISBN)
Disputas
2011-02-04, Häggsalen, Ångström laboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (engelsk)
Opponent
Veileder
Merknad
Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 726Tilgjengelig fra: 2011-01-14 Laget: 2010-12-19 Sist oppdatert: 2011-03-21bibliografisk kontrollert
2. Aqueous Solutions as seen through an Electron Spectrometer: Surface Structure, Hydration Motifs and Ultrafast Charge Delocalization Dynamics
Åpne denne publikasjonen i ny fane eller vindu >>Aqueous Solutions as seen through an Electron Spectrometer: Surface Structure, Hydration Motifs and Ultrafast Charge Delocalization Dynamics
2011 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
Abstract [en]

In spite of their high abundance and importance, aqueous systems are enigmatic on the microscopic scale. In order to obtain information about their geometrical and electronic structure, simple aqueous solutions have been studied experimentally by photo- and Auger electron spectroscopy using the novel liquid micro-jet technique in conjunction with synchrotron radiation. The thesis is thematically divided into three parts.

In the first part we utilize the surface sensitivity of photoelectron spectroscopy to probe the distributions of solutes near the water surface. In agreement with recent theoretical predictions we find that large polarizable anions, such as I- and ClO4-, display enhanced surface propensities compared to smaller rigid ions. Surface effects arising from ion-ion interactions at higher electrolyte concentrations and as function of pH are investigated. Studies of linear mono-carboxylic acids and benzoic acid show that the neutral molecular forms of such weak acids are better stabilized at the water surface than their respective conjugate base forms.

The second part examines what type of information core-electron spectra can yield about the chemical state and hydration structure of small organic molecules in water. We demonstrate that the method is sensitive to the protonation state of titratable functional groups and that core-level lineshapes are dependent on local water hydration configurations. Using a combination of photoelectron and X-ray absorption spectroscopy we also show that the electronic re-arrangement upon hydrolysis of aldehydes yields characteristic fingerprints in core-level spectra.

In the last part of this thesis we study ultrafast charge delocalization dynamics in aqueous solutions using resonant and off-resonant Auger spectroscopy. Intermolecular Coulombic decay (ICD) is found to occur in a number of core-excited solutions where excess energy is transferred between the solvent and the solute. The rate of ultrafast electron delocalization between hydrogen bonded water molecules upon oxygen 1s resonant core-excitation is found to decrease upon solvation of inorganic ions.

The presented work is illustrative of how core-level photoelectron spectroscopy can be valuable in the study of fundamental phenomena in aqueous solutions.

sted, utgiver, år, opplag, sider
Uppsala: Acta Universitatis Upsaliensis, 2011. s. 118
Serie
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 828
Emneord
Water, Aqueous solutions, Ions, Molecular Hydration, Electron dynamics, Atmospheric Chemistry, Hydrolysis, Acid-Base Chemistry, Interatomic Coulombic Decay, ICD, Liquid Micro-Jet, X-ray Photoelectron Spectroscopy, XPS, Auger Electron Spectroscopy, AES, MAX-lab, BESSY
HSV kategori
Forskningsprogram
Fysik med inriktning mot atom- molekyl- och kondenserande materiens fysik
Identifikatorer
urn:nbn:se:uu:diva-151435 (URN)978-91-554-8083-7 (ISBN)
Disputas
2011-06-01, Polhemssalen, Ångström Laboratory, Lägerhyddsvägen 1, Uppsala, 10:15 (engelsk)
Opponent
Veileder
Tilgjengelig fra: 2011-05-11 Laget: 2011-04-11 Sist oppdatert: 2011-07-01bibliografisk kontrollert

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