| 1. |
- Atak, Kaan, et al.
(författare)
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The Chemical Bond in Carbonyl and Sulfinyl Groups Studied by Soft X-ray Spectroscopy and ab Initio Calculations
- 2012
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Ingår i: ChemPhysChem. - : Wiley. - 1439-4235 .- 1439-7641. ; 13:13, s. 3106-3111
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Tidskriftsartikel (refereegranskat)abstract
- The polar character of the sulfinyl bond, which determines many of the properties of dimethyl sulfoxide (DMSO), is a result of charge transfer in low-lying π-type orbitals. This characteristic—together with the wide energy gap between the highest occupied and the lowest unoccupied molecular orbitals of this substance—makes DMSO a relatively inert aprotic solvent with strong nucleophilicity and electrophilicity.
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| 2. |
- Engel, Nicholas, et al.
(författare)
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DMSO-Water Clustering in Solution Observed in Soft X-ray Spectra
- 2012
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Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 3:24, s. 3697-3701
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Tidskriftsartikel (refereegranskat)abstract
- The significant deviation from the ideality of dimethyl sulfoxide (DMSO)/water mixtures can be addressed based on the change of the local molecular orbitals of each solvent upon mixing. Oxygen K-edge absorption and emission spectra of DMSO/water solutions were measured using the liquid microjet technique. The spectra demonstrate that the hydrogen bond network in liquid water is already influenced at small DMSO concentrations, and at the molar fraction x(DMSO) = 0.43 we find strong evidence of DMSO-water clustering reflected by the influence on the occupied molecular orbitals.
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| 3. |
- Lange, Kathrin M., et al.
(författare)
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On the Origin of the Hydrogen-Bond-Network Nature of Water : X-Ray Absorption and Emission Spectra of Water-Acetonitrile Mixtures
- 2011
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 50:45, s. 10621-10625
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Tidskriftsartikel (refereegranskat)abstract
- A liquid microjet was used to obtain oxygen K-edge X-ray absorption and emission spectra of water–acetonitrile mixtures of various compositions. The observed spectral changes are unambiguously related to the increasing number of broken hydrogen bonds with decreasing water concentration, and the hydrogen-bond network of liquid water can thus be addressed on purely experimental grounds without the need for theoretical modeling.
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| 4. |
- Lange, Kathrin M., et al.
(författare)
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X-ray emission from pure and dilute H2O and D2O in a liquid microjet : Hydrogen bonds and nuclear dynamics
- 2012
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 85:15, s. 155104-
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Tidskriftsartikel (refereegranskat)abstract
- Knowledge about the hydrogen bond network of water is essential for understanding its anomalies as well as its special role for biochemical systems. Different types of x-ray spectroscopy allow probing of the molecular orbitals of water, revealing the electronic structure which reflects the hydrogen bond conformations. In this work a recently developed high-resolution x-ray emission spectrometer was used in combination with the microjet technique for recording spectra of liquid H2O and D2O and their mixtures with acetonitrile. Variation of the nuclear dynamics via isotope substitution and variation of the hydrogen bond conformation via dissolution in acetonitrile was investigated. These two effects have two clearly distinguishable spectral fingerprints.
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| 5. |
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