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The principles of infrared-x-ray pump-probe spectroscopy. Applications on proton transfer in core-ionized water dimers
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).
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2005 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 122, no 9, 094319Article in journal (Refereed) Published
Abstract [en]

In this paper we derive the basic physics underlying infrared-x-ray pump-probe spectroscopy (IR, infrared). Particular features of the spectroscopy are highlighted and discussed, such as dependence on phase of the infrared pulse, duration and delay time of the x-ray pulse, and molecular orientation. Numerical applications are carried out for the water dimer using wave packet techniques. It is shown that core ionization of the donor oxygen of the water dimer results in a drastic change of the potential with the global minimum placed in the proton transfer region. The results of the modeling indicate that IR-x-ray pump-probe spectroscopy can be used to study the dynamics of proton transfer in this core-ionized state, and that, contrary to conventional core level photoelectron spectroscopy, x-ray core-ionization driven by an IR field is a proper method to explore the proton transfer in a system like the water dimer. We observe that the trajectory of the nuclear wave packet in the ground state potential well is strongly affected by the absolute phase of the IR pulse.

Place, publisher, year, edition, pages
American Institute of Physics (AIP), 2005. Vol. 122, no 9, 094319
Keyword [en]
Dimers, Ionization, Nuclear energy, Protons, Quantum theory, Watersheds
National Category
Physical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-24955DOI: 10.1063/1.1860312ISI: 000227483300040PubMedID: 15836140Scopus ID: 2-s2.0-22944466386OAI: oai:DiVA.org:kth-24955DiVA: diva2:354605
Note

QC 20101004

Available from: 2010-10-04 Created: 2010-10-04 Last updated: 2017-12-12Bibliographically approved
In thesis
1. Principles of Infrared - X-ray Pump-probe Spectroscopy
Open this publication in new window or tab >>Principles of Infrared - X-ray Pump-probe Spectroscopy
2006 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

The present thesis concerns theoretical studies of molecular interactions investigated by infrared and X-ray spectroscopic techniques, with emphasis on using these two techniques combined in pump-probe experiments. Four main types of studies are addressed: the use of near-edge X-ray absorption fine structure spectra (NEXAFS) to manifest through-bond and through-space interactions; the role of hydrogen bonding in the formation of X-ray photoelectron spectra as evidenced by simulations of the water dimer; the development of theory, with sample applications, for infrared X-ray pump-probe spectroscopy; and molecular dynamics simulations of light-induced fragmentation of water clusters.

Ab initio calculations indicate that NEXAFS spectra give direct information about the through-bond and through-space interactions between vacant non-conjugated π* orbitals. It is found out that the X-ray photoelectron spectrum of the water dimer differs dramatically from the monomer spectrum in that two bands are observed, separated by the chemically shifted ionization potentials of the donor and the acceptor. The hydrogen bond is responsible for the anomalously strong broadening of these two bands. The studies show that X-ray core electron ionization of the water dimer driven by an infrared field is a proper technique to prove the proton transfered state contrary to conventional X-ray photoelectron spectroscopy.

The physical aspects of the proposed new X-ray spectroscopic method - phase sensitive Infrared - X-Ray Pump-Probe Spectroscopy - are examined in detail using the wave packet technique in three applications; the NO molecule and the dynamics of proton transfer in core ionized water dimer and glyoxalmonoxime. It is found out that the phase of the infrared pump field strongly influences the trajectory of the nuclear wave packet on the ground state potential, which results in a phase dependence of the X-ray pump-probe spectra. A proper choice of the delay time of the X-ray pulse allows the direct observation of the X-ray transition in the proton transfered well of the core excited potential. It is found out that the glyoxalmonoxime molecule possesses an important feature; proton transfer accompanied by core hole hopping. Special attention is paid to the quantum control of the populations of vibrational level which is of crucial importance to shape the wave packet of desirable size.

The wave packet technique becomes computationally very expensive when the number of nuclear degrees of freedom is large. Molecular dynamics is used instead in studies of light-induced nuclear kinetics in the water hexamer cluster. We predict a novel mechanism of the mechanical action of light on atoms and molecules. This mechanism is based on the rectification of the Lorentz force, which gives a unique opportunity of direct site selective mechanical action of light on atoms and molecules inside large systems like clusters or biomolecules.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2006. x, 66 p.
National Category
Industrial Biotechnology
Identifiers
urn:nbn:se:kth:diva-4245 (URN)978-91-7178-508-4 (ISBN)
Public defence
2006-12-20, FA32, AlbaNova, Roslagstullsbacken 21, Stockholm, 10:00
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Note

QC 20170222

Available from: 2006-12-15 Created: 2006-12-15 Last updated: 2017-02-22Bibliographically approved

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Ågren, Hans

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