TY  - JOUR
A1  - Yin, Zhong
A1  - Rajkovic, Ivan
A1  - Veedu, Sreevidya Thekku
A1  - Deinert, Sascha
A1  - Raiser, Dirk
A1  - Jain, Rohit
A1  - Fukuzawa, Hironobu
A1  - Wada, Shin-ichi
A1  - Quevedo, Wilson
A1  - Kennedy, Brian
A1  - Schreck, Simon
A1  - Pietzsch, Annette
A1  - Wernet, Philippe
A1  - Ueda, Kyoshi
A1  - Föhlisch, Alexander
A1  - Techert, Simone
T1  - Ionic solutions probed by resonant inelastic X-ray scattering
JF  - Zeitschrift für physikalische Chemie : international journal of research in physical chemistry and chemical physics
N2  - X-ray spectroscopy is a powerful tool to study the local charge distribution of chemical systems. Together with the liquid jet it becomes possible to probe chemical systems in their natural environment, the liquid phase. In this work, we present X-ray absorption (XA), X-ray emission (XE) and resonant inelastic X-ray scattering (RIXS) data of pure water and various salt solutions and show the possibilities these methods offer to elucidate the nature of ion-water interaction.
KW  - X-ray Spectroscopy
KW  - XAS
KW  - XES
KW  - RIXS
KW  - Anions
KW  - Cations
KW  - Liquid Jet
KW  - Synchrotron Radiation
Y1  - 2015
U6  - https://doi.org/10.1515/zpch-2015-0610
SN  - 0942-9352
VL  - 229
IS  - 10-12
SP  - 1855
EP  - 1867
PB  - De Gruyter
CY  - Berlin
ER  - 
TY  - JOUR
A1  - Yin, Zhong
A1  - Rajkovic, Ivan
A1  - Kubicek, Katharina
A1  - Quevedo, Wilson
A1  - Pietzsch, Annette
A1  - Wernet, Philippe
A1  - Föhlisch, Alexander
A1  - Techert, Simone
T1  - Probing the Hofmeister effect with ultrafast core-hole spectroscopy
JF  - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry
N2  - In the current work, X-ray emission spectra of aqueous solutions of different inorganic salts within the Hofmeister series are presented. The results reflect the direct interaction of the ions with the water molecules and therefore, reveal general properties of the salt-water interactions. Within the experimental precision a significant effect of the ions on the water structure has been observed but no ordering according to the structure maker/structure breaker concept could be mirrored in the results indicating that the Hofmeister effect if existent may be caused by more complex interactions.
Y1  - 2014
U6  - https://doi.org/10.1021/jp504577a
SN  - 1520-6106
VL  - 118
IS  - 31
SP  - 9398
EP  - 9403
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Yin, Zhong
A1  - Inhester, Ludger
A1  - Veedu, Sreevidya Thekku
A1  - Quevedo, Wilson
A1  - Pietzsch, Annette
A1  - Wernet, Philippe
A1  - Groenhof, Gerrit
A1  - Föhlisch, Alexander
A1  - Grubmueller, Helmut
A1  - Techert, Simone
T1  - Cationic and Anionic Impact on the Electronic Structure of Liquid Water
JF  - The journal of physical chemistry letters
N2  - Hydration shells around ions are crucial for many fundamental biological and chemical processes. Their local physicochemical properties are quite different from those of bulk water and hard to probe experimentally. We address this problem by combining soft X-ray spectroscopy using a liquid jet and molecular dynamics (MD) simulations together with ab initio electronic structure calculations to elucidate the water ion interaction in a MgCl2 solution at the molecular level. Our results reveal that salt ions mainly affect the electronic properties of water molecules in close vicinity and that the oxygen K-edge X-ray emission spectrum of water molecules in the first solvation shell differs significantly from that of bulk water. Ion-specific effects are identified by fingerprint features in the water X-ray emission spectra. While Mg2+ ions cause a bathochromic shift of the water lone pair orbital, the 3p orbital of the Cl- ions causes an additional peak in the water emission spectrum at around 528 eV.
Y1  - 2017
U6  - https://doi.org/10.1021/acs.jpclett.7b01392
SN  - 1948-7185
VL  - 8
SP  - 3759
EP  - 3764
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Wernet, Philippe
A1  - Kunnus, Kristjan
A1  - Schreck, Simon
A1  - Quevedo, Wilson
A1  - Kurian, Reshmi
A1  - Techert, Simone
A1  - de Groot, Frank M. F.
A1  - Odelius, Michael
A1  - Föhlisch, Alexander
T1  - Dissecting local atomic and intermolecular interactions of transition-metal ions in solution with selective X-ray spectroscopy
JF  - The journal of physical chemistry letters
N2  - Determining covalent and charge-transfer contributions to bonding in solution has remained an experimental challenge. Here, the quenching of fluorescence decay channels as expressed in dips in the L-edge X-ray spectra of solvated 3d transition-metal ions and complexes was reported as a probe. With a full set of experimental and theoretical ab initio L-edge X-ray spectra of aqueous Cr3+, including resonant inelastic X-ray scattering, we address covalency and charge transfer for this prototypical transition-metal ion in solution. We dissect local atomic effects from intermolecular interactions and quantify X-ray optical effects. We find no evidence for the asserted ultrafast charge transfer to the solvent and show that the dips are readily explained by X-ray optical effects and local atomic state dependence of the fluorescence yield. Instead, we find, besides ionic interactions, a covalent contribution to the bonding in the aqueous complex of ligand-to-metal charge-transfer character.
Y1  - 2012
U6  - https://doi.org/10.1021/jz301486u
SN  - 1948-7185
VL  - 3
IS  - 23
SP  - 3448
EP  - 3453
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Wernet, Philippe
A1  - Kunnus, Kristjan
A1  - Josefsson, Ida
A1  - Rajkovic, Ivan
A1  - Quevedo, Wilson
A1  - Beye, Martin
A1  - Schreck, Simon
A1  - Gruebel, S.
A1  - Scholz, Mirko
A1  - Nordlund, Dennis
A1  - Zhang, Wenkai
A1  - Hartsock, Robert W.
A1  - Schlotter, William F.
A1  - Turner, Joshua J.
A1  - Kennedy, Brian
A1  - Hennies, Franz
A1  - de Groot, Frank M. F.
A1  - Gaffney, Kelly J.
A1  - Techert, Simone
A1  - Odelius, Michael
A1  - Föhlisch, Alexander
T1  - Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)(5) in solution
JF  - Nature : the international weekly journal of science
N2  - Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion(1,2). Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site(3-11) that need to be controlled to optimize complexes for photocatalytic hydrogen production(8) and selective carbon-hydrogen bond activation(9-11). An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond-resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)(5) in solution, that the photo-induced removal of CO generates the 16-electron Fe(CO)(4) species, a homogeneous catalyst(12,13) with an electron deficiency at the Fe centre(14,15), in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)(5) (refs 4, 16-20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.
Y1  - 2015
U6  - https://doi.org/10.1038/nature14296
SN  - 0028-0836
SN  - 1476-4687
VL  - 520
IS  - 7545
SP  - 78
EP  - 81
PB  - Nature Publ. Group
CY  - London
ER  - 
TY  - JOUR
A1  - Schreck, Simon
A1  - Pietzsch, Annette
A1  - Kunnus, Kristjan
A1  - Kennedy, Brian
A1  - Quevedo, Wilson
A1  - Miedema, Piter S.
A1  - Wernet, Philippe
A1  - Föhlisch, Alexander
T1  - Dynamics of the OH group and the electronic structure of liquid alcohols
JF  - Structural dynamics
N2  - In resonant inelastic soft x-ray scattering (RIXS) from molecular and liquid systems, the interplay of ground state structural and core-excited state dynamical contributions leads to complex spectral shapes that partially allow for ambiguous interpretations. In this work, we dissect these contributions in oxygen K-edge RIXS from liquid alcohols. We use the scattering into the electronic ground state as an accurate measure of nuclear dynamics in the intermediate core-excited state of the RIXS process. We determine the characteristic time in the core-excited state until nuclear dynamics give a measurable contribution to the RIXS spectral profiles to tau(dyn) = 1.2 +/- 0.8 fs. By detuning the excitation energy below the absorption resonance we reduce the effective scattering time below sdyn, and hence suppress these dynamical contributions to a minimum. From the corresponding RIXS spectra of liquid methanol, we retrieve the "dynamic-free" density of states and find that it is described solely by the electronic states of the free methanol molecule. From this and from the comparison of normal and deuterated methanol, we conclude that the split peak structure found in the lone-pair emission region at non-resonant excitation originates from dynamics in the O-H bond in the core-excited state. We find no evidence that this split peak feature is a signature of distinct ground state structural complexes in liquid methanol. However, we demonstrate how changes in the hydrogen bond coordination within the series of linear alcohols from methanol to hexanol affect the split peak structure in the liquid alcohols. (C) 2014 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.
Y1  - 2014
U6  - https://doi.org/10.1063/1.4897981
SN  - 2329-7778
VL  - 1
IS  - 5
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - GEN
A1  - Niskanen, Johannes
A1  - Kooser, Kuno
A1  - Koskelo, Jaakko
A1  - Käämbre, Tanel
A1  - Kunnus, Kristjan
A1  - Pietzsch, Annette
A1  - Quevedo, Wilson
A1  - Hakala, Mikko
A1  - Föhlisch, Alexander
A1  - Huotari, Simo
A1  - Kukk, Edwin
T1  - Density functional simulation of resonant inelastic X-ray scattering experiments in liquids: acetonitrile
N2  - In this paper we report an experimental and computational study of liquid acetonitrile (H3C–C[triple bond, length as m-dash]N) by resonant inelastic X-ray scattering (RIXS) at the N K-edge. The experimental spectra exhibit clear signatures of the electronic structure of the valence states at the N site and incident-beam-polarization dependence is observed as well. Moreover, we find fine structure in the quasielastic line that is assigned to finite scattering duration and nuclear relaxation. We present a simple and light-to-evaluate model for the RIXS maps and analyze the experimental data using this model combined with ab initio molecular dynamics simulations. In addition to polarization-dependence and scattering-duration effects, we pinpoint the effects of different types of chemical bonding to the RIXS spectrum and conclude that the H2C–C[double bond, length as m-dash]NH isomer, suggested in the literature, does not exist in detectable quantities. We study solution effects on the scattering spectra with simulations in liquid and in vacuum. The presented model for RIXS proved to be light enough to allow phase-space-sampling and still accurate enough for identification of transition lines in physical chemistry research by RIXS.
T3  - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 331 
Y1  - 2016
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-395133
ER  - 
TY  - JOUR
A1  - Mitzner, Rolf
A1  - Rehanek, Jens
A1  - Kern, Jan
A1  - Gul, Sheraz
A1  - Hattne, Johan
A1  - Taguchi, Taketo
A1  - Alonso-Mori, Roberto
A1  - Tran, Rosalie
A1  - Weniger, Christian
A1  - Schröder, Henning
A1  - Quevedo, Wilson
A1  - Laksmono, Hartawan
A1  - Sierra, Raymond G.
A1  - Han, Guangye
A1  - Lassalle-Kaiser, Benedikt
A1  - Koroidov, Sergey
A1  - Kubicek, Katharina
A1  - Schreck, Simon
A1  - Kunnus, Kristjan
A1  - Brzhezinskaya, Maria
A1  - Firsov, Alexander
A1  - Minitti, Michael P.
A1  - Turner, Joshua J.
A1  - Möller, Stefan
A1  - Sauter, Nicholas K.
A1  - Bogan, Michael J.
A1  - Nordlund, Dennis
A1  - Schlotter, William F.
A1  - Messinger, Johannes
A1  - Borovik, Andrew S.
A1  - Techert, Simone
A1  - de Groot, Frank M. F.
A1  - Föhlisch, Alexander
A1  - Erko, Alexei
A1  - Bergmann, Uwe
A1  - Yachandra, Vittal K.
A1  - Wernet, Philippe
A1  - Yano, Junko
T1  - L-edge x-ray absorption spectroscopy of dilute systems relevant to metalloproteins using an X-ray free-electron laser
JF  - The journal of physical chemistry letters
N2  - L-edge spectroscopy of 3d transition metals provides important electronic structure information and has been used in many fields. However, the use of this method for studying dilute aqueous systems, such as metalloenzymes, has not been prevalent because of severe radiation damage and the lack of suitable detection systems. Here we present spectra from a dilute Mn aqueous solution using a high-transmission zone-plate spectrometer at the Linac Coherent Light Source (LCLS). The spectrometer has been optimized for discriminating the Mn L-edge signal from the overwhelming 0 K-edge background that arises from water and protein itself, and the ultrashort LCLS X-ray pulses can outrun X-ray induced damage. We show that the deviations of the partial-fluorescence yield-detected spectra from the true absorption can be well modeled using the state-dependence of the fluorescence yield, and discuss implications for the application of our concept to biological samples.
Y1  - 2013
U6  - https://doi.org/10.1021/jz401837f
SN  - 1948-7185
VL  - 4
IS  - 21
SP  - 3641
EP  - 3647
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Kunnus, Kristjan
A1  - Zhang, Wenkai
A1  - Delcey, Mickael G.
A1  - Pinjari, Rahul V.
A1  - Miedema, Piter S.
A1  - Schreck, Simon
A1  - Quevedo, Wilson
A1  - Schröder, Henning
A1  - Föhlisch, Alexander
A1  - Gaffney, Kelly J.
A1  - Lundberg, Marcus
A1  - Odelius, Michael
A1  - Wernet, Philippe
T1  - Viewing the Valence Electronic Structure of Ferric and Ferrous Hexacyanide in Solution from the Fe and Cyanide Perspectives
JF  - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry
N2  - The valence-excited states of ferric and ferrous hexacyanide ions in aqueous solution were mapped by resonant inelastic X-ray scattering (RIXS) at the Fe L-2,L-3 and N K edges. Probing of both the central Fe and the ligand N atoms enabled identification of the metal-and ligand-centered excited states, as well as ligand-to-metal and metal-to-ligand charge-transfer excited states. Ab initio calculations utilizing the RASPT2 method were used to simulate the Fe L-2,L-3-edge RIXS spectra and enabled quantification of the covalencies of both occupied and empty orbitals of pi and sigma symmetry. We found that pi back-donation in the ferric complex is smaller than that in the ferrous complex. This is evidenced by the relative amounts of Fe 3d character in the nominally 2 pi CN- molecular orbital of 7% and 9% in ferric and ferrous hexacyanide, respectively. Utilizing the direct sensitivity of Fe L-3-edge RIXS to the Fe 3d character in the occupied molecular orbitals, we also found that the donation interactions are dominated by sigma bonding. The latter was found to be stronger in the ferric complex, with an Fe 3d contribution to the nominally 5 sigma CN- molecular orbitals of 29% compared to 20% in the ferrous complex. These results are consistent with the notion that a higher charge at the central metal atom increases donation and decreases back-donation.
Y1  - 2016
U6  - https://doi.org/10.1021/acs.jpcb.6b04751
SN  - 1520-6106
VL  - 120
SP  - 7182
EP  - 7194
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Kunnus, Kristjan
A1  - Rajkovic, Ivan
A1  - Schreck, Simon
A1  - Quevedo, Wilson
A1  - Eckert, Sebastian Oliver
A1  - Beye, Martin
A1  - Suljoti, Edlira
A1  - Weniger, Christian
A1  - Kalus, Christian
A1  - Gruebel, Sebastian
A1  - Scholz, Mirko
A1  - Nordlund, Dennis
A1  - Zhang, Wenkai
A1  - Hartsock, Robert W.
A1  - Gaffney, Kelly J.
A1  - Schlotter, William F.
A1  - Turner, Joshua J.
A1  - Kennedy, Brian
A1  - Hennies, Franz
A1  - Techert, Simone
A1  - Wernet, Philippe
A1  - Föhlisch, Alexander
T1  - A setup for resonant inelastic soft x-ray scattering on liquids at free electron laser light sources
JF  - Review of scientific instruments : a monthly journal devoted to scientific instruments, apparatus, and techniques
N2  - We present a flexible and compact experimental setup that combines an in vacuum liquid jet with an x-ray emission spectrometer to enable static and femtosecond time-resolved resonant inelastic soft x-ray scattering (RIXS) measurements from liquids at free electron laser (FEL) light sources. We demonstrate the feasibility of this type of experiments with the measurements performed at the Linac Coherent Light Source FEL facility. At the FEL we observed changes in the RIXS spectra at high peak fluences which currently sets a limit to maximum attainable count rate at FELs. The setup presented here opens up new possibilities to study the structure and dynamics in liquids.
Y1  - 2012
U6  - https://doi.org/10.1063/1.4772685
SN  - 0034-6748
VL  - 83
IS  - 12
PB  - American Institute of Physics
CY  - Melville
ER  -