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Local Structure of Hydrogen-Bonded Liquids
Stockholm University, Faculty of Science, Department of Physics.
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Ordinary yet unique, water is the substance on which life is based. Water seems, at first sight, to be a very simple molecule, consisting of two hydrogen atoms attached to one oxygen. Its small size belies the complexity of its action and its numerous anomalies, central to a broad class of important phenomena, ranging from global current circulation, terrestrial water and CO2 cycles to corrosion and wetting. The explanation of this complex behavior comes from water's unique ability to form extensive three-dimensional networks of hydrogen-bonds, whose nature and structures, in spite of a great deal of efforts involving a plethora of experimental and theoretical techniques, still lacks a complete scientific understanding.

This thesis is devoted to the study of the local structure of hydrogen-bonded liquids, with a particular emphasis on water, taking advantage of a combination of core-level spectroscopies and density functional theory spectra calculations. X-ray absorption, in particular, is found to be sensitive to the local hydrogen-bond environment, thus offering a very promising tool for spectroscopic identification of specific structural configurations in water, alcohols and aqueous solutions. More specifically, the characteristic spectroscopic signature of the broken hydrogen-bond at the hydrogen side is used to analyze the structure of bulk water, leading to the finding that most molecules are arranged in two hydrogen-bond configurations, in contrast to the picture provided by molecular dynamics simulations. At the liquid-vapor interface, an interplay of surface sensitive measurements and theoretical calculations enables us to distinguish a new interfacial species in equilibrium with the gas. In a similar approach the cluster form of the excess proton in highly concentrated acid solutions and the different coordination of methanol at the vacuum interface and in the bulk can also be clearly identified.

Finally the ability of core-level spectroscopies, aided by sophisticated density functional theory calculations, to directly probe the valence electronic structure of a system is used to observe the nature of the interaction between water molecules and solvated ions in solution. Water around transition metal ions is found to interact with the solute via orbital mixing with the metal d-orbitals. The hydrogen-bond between water molecules is explained in terms of electrostatic interactions enhanced by charge rehybridization in which charge transfer between connecting molecules is shown to be fundamental.

Place, publisher, year, edition, pages
Stockholm: Fysikum , 2004. , 66 p.
Keyword [en]
hydrogen-bond, water, ice, density functional theory, DFT, core-level spectroscopies, x-ray absorption
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-286ISBN: 91-7265-969-6 (print)OAI: oai:DiVA.org:su-286DiVA: diva2:191969
Public defence
2004-12-08, sal FA32, AlbaNova universitetscentrum, Roslagstullsbacken 21, Stockholm, 10:00
Opponent
Supervisors
Available from: 2004-11-17 Created: 2004-11-17Bibliographically approved
List of papers
1. Spectroscopic probing of local hydrogen-bonding structures in liquid water
Open this publication in new window or tab >>Spectroscopic probing of local hydrogen-bonding structures in liquid water
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2002 In: J. Phys. Cond. Matt., ISSN 0953-8984, Vol. 14, no 8, L213-219 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23403 (URN)
Note
Part of urn:nbn:se:su:diva-286Available from: 2004-11-17 Created: 2004-11-17Bibliographically approved
2. Characterization of hydrogen bond acceptor molecules at the water surface using near-edge x-ray absorption fine-structure spectroscopy and density functional theory
Open this publication in new window or tab >>Characterization of hydrogen bond acceptor molecules at the water surface using near-edge x-ray absorption fine-structure spectroscopy and density functional theory
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2002 In: J. Phys. Cond. Matt., ISSN 0953-8984, Vol. 14, no 8, L221-L226 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23404 (URN)
Note
Part of urn:nbn:se:su:diva-286Available from: 2004-11-17 Created: 2004-11-17Bibliographically approved
3. The structure of the first coordination shell in liquid water
Open this publication in new window or tab >>The structure of the first coordination shell in liquid water
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2004 In: Science, ISSN 0036-8075, Vol. 304, no 5673, 995-999 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23405 (URN)
Note
Part of urn:nbn:se:su:diva-286Available from: 2004-11-17 Created: 2004-11-17Bibliographically approved
4. Modeling the x-ray absorption spectrum of liquid water by molecular dynamics simulations
Open this publication in new window or tab >>Modeling the x-ray absorption spectrum of liquid water by molecular dynamics simulations
Manuscript (Other academic)
Identifiers
urn:nbn:se:su:diva-23406 (URN)
Funder
Note
Part of urn:nbn:se:su:diva-286Available from: 2004-11-17 Created: 2004-11-17 Last updated: 2010-12-23
5. Half or full core hole in density functional theory X-ray absorption spectrum calculations of water?
Open this publication in new window or tab >>Half or full core hole in density functional theory X-ray absorption spectrum calculations of water?
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2005 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 7, no 15, 2854-2858 p.Article in journal (Refereed) Published
Abstract [en]

We analyze the performance of two different core-hole potentials in the theoretical modeling of XAS of ice, liquid and gas phase water; the use of a full core-hole (FCH) in the calculations, as suggested by Hetenyi et al. [B. Hetenyi, F. De Angelis, P. Giamozzi and R. Car, J. Chem. Phys., 2004, 120(18), 8632], gives poor agreement with experiment in terms of intensity distribution as well as transition energies, while the half core hole (HCH) potential, in the case of water, provides a better compromise between initial and final state effects, leading to good agreement with the experimental data.

National Category
Natural Sciences
Identifiers
urn:nbn:se:su:diva-23407 (URN)10.1039/b505723j (DOI)
Note
Part of urn:nbn:se:su:diva-286Available from: 2004-11-17 Created: 2004-11-17 Last updated: 2017-12-13Bibliographically approved
6. X-absorption spectra of water within a plane-wave Car-Parrinello molecular dynamics framework
Open this publication in new window or tab >>X-absorption spectra of water within a plane-wave Car-Parrinello molecular dynamics framework
2004 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 121, no 20, 10065-10075 p.Article in journal (Refereed) Submitted
Abstract [en]

We describe the implementation of a simple technique to simulate core-level spectra within the Car-Parrinello plane-waves molecular dynamics framework. The x-ray absorption (XA) spectra are generated using the transition potential technique with the effect of the core hole included through a specifically developed pseudopotential for the core-excited atom. Despite the lack of 1s core orbitals in the pseudopotential treatment, the required transition moments are accurately calculated without reconstruction of the all-electron orbitals. The method is applied to the oxygen XA spectra of water in its various aggregation states, but it is transferable to any first-row element. The computed spectra are compared favorably with the results from all-electron cluster calculations, as well as with experimental data. The periodicity of the plane-wave technique improves the description of condensed phases. The molecular dynamics simulation enables in principle a proper treatment of thermal effects and dynamical averaging in complex systems.

Place, publisher, year, edition, pages
American Institute of Physics, 2004
Keyword
X-ray absorption spectra, water, molecular dynamics method, core levels, pseudopotential methods, transition moments, molecular electronic states, APW calculations, spectroscopy computing
National Category
Physical Sciences
Identifiers
urn:nbn:se:su:diva-23408 (URN)10.1063/1.1807821 (DOI)
Note
Part of urn:nbn:se:su:diva-286Available from: 2004-11-17 Created: 2004-11-17 Last updated: 2017-12-13Bibliographically approved
7. X-ray absorption signature of protonated clusters in acid solution
Open this publication in new window or tab >>X-ray absorption signature of protonated clusters in acid solution
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Manuscript (Other academic)
Identifiers
urn:nbn:se:su:diva-23409 (URN)
Note
Part of urn:nbn:se:su:diva-286Available from: 2004-11-17 Created: 2004-11-17 Last updated: 2010-01-13Bibliographically approved
8. X-ray absorption spectroscopy of liquid methanol microjets: surface vs. bulk electronic structure and hydrogen bonding
Open this publication in new window or tab >>X-ray absorption spectroscopy of liquid methanol microjets: surface vs. bulk electronic structure and hydrogen bonding
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2005 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 109, no 20, 10194-10203 p.Article in journal (Refereed) Published
Abstract [en]

We have measured the X-ray absorption (XA) spectrum of liquid (298 K) methanol at the oxygen and carbon K edges. The 4a1 orbital at the O K edge exhibits a pronounced sensitivity to the formation of intermolecular hydrogen bonds, with significant differences observed between the vapor and bulk spectra, whereas the C K edge reveals only subtle corresponding spectral changes. Comparison with DFT computed spectra of model methanol clusters indicates that the bulk liquid comprises long chains (n > 6) and rings of hydrogen-bonded monomers.

National Category
Physical Sciences
Identifiers
urn:nbn:se:su:diva-23410 (URN)10.1021/jp049278u (DOI)
Note
Part of urn:nbn:se:su:diva-286Available from: 2004-11-17 Created: 2004-11-17 Last updated: 2017-12-13Bibliographically approved
9. Direct evidence of orbital mixing between water and solvated transition-metal ions: An oxygen 1s XAS and DFT study of aqueous systems
Open this publication in new window or tab >>Direct evidence of orbital mixing between water and solvated transition-metal ions: An oxygen 1s XAS and DFT study of aqueous systems
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2003 In: J. Chem. Phys. A, ISSN 1089-5639, Vol. 107, no 35, 6869-6876 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23411 (URN)
Note
Part of urn:nbn:se:su:diva-286Available from: 2004-11-17 Created: 2004-11-17Bibliographically approved
10. The interpretation of X-ray absorption spectra of water and ice
Open this publication in new window or tab >>The interpretation of X-ray absorption spectra of water and ice
2002 In: Chem. Phys. Lett., ISSN 0009-2614, Vol. 364, no 3-4, 363-370 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23412 (URN)
Note
Part of urn:nbn:se:su:diva-286Available from: 2004-11-17 Created: 2004-11-17Bibliographically approved
11. The hydrogen bond in ice probed by soft x-ray spectroscopy and density functional theory
Open this publication in new window or tab >>The hydrogen bond in ice probed by soft x-ray spectroscopy and density functional theory
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2005 (English)In: Journal of Chemical Physics, ISSN 1089-7690, Vol. 122, 154505- p.Article in journal (Refereed) Published
Abstract [en]

We combine photoelectron and x-ray absorption spectroscopy with density functional theory to derive a molecular orbital picture of the hydrogen bond in ice. We find that the hydrogen bond involves donation and back-donation of charge between the oxygen lone pair and the O–H antibonding orbitals on neighboring molecules. Together with internal s-p rehybridization this minimizes the repulsive charge overlap of the connecting oxygen and hydrogen atoms, which is essential for a strong attractive electrostatic interaction. Our joint experimental and theoretical results demonstrate that an electrostatic model based on only charge induction from the surrounding medium fails to properly describe the internal charge redistributions upon hydrogen bonding.

Place, publisher, year, edition, pages
American Institute of Physics, 2005
Keyword
ice, hydrogen bonds, X-ray absorption spectra, density functional theory, photoelectron spectra, molecular electronic states, oxygen compounds
National Category
Physical Sciences
Research subject
Chemical Physics
Identifiers
urn:nbn:se:su:diva-23413 (URN)10.1063/1.1879752 (DOI)
Note
Part of urn:nbn:se:su:diva-286Available from: 2004-11-17 Created: 2004-11-17 Last updated: 2010-01-22Bibliographically approved

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