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Proton transfer mediated by the vibronic coupling in oxygen core ionized states of glyoxalmonoxime studied by infrared-X-ray pump-probe spectroscopy.
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512). Universidade Federal de Minas Gerais, Brazil.
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512). Universidade Federal de Minas Gerais, Brazil.
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).
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2006 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 110, no 47, 12805-12813 p.Article in journal (Refereed) Published
Abstract [en]

The theory of IR-X-ray pump-probe spectroscopy beyond the Born-Oppenheimer approximation is developed and applied to the study of the dynamics of intramolecular proton transfer in glyoxalmonoxime leading to the formation of the tautomer 2-nitrosoethenol. Due to the IR pump pulses the molecule gains sufficient energy to promote a proton to a weakly bound well. A femtosecond X-ray pulse snapshots the wave packet route and, hence, the dynamics of the proton transfer. The glyoxalmonoxime molecule contains two chemically nonequivalent oxygen atoms that possess distinct roles in the hydrogen bond, a hydrogen donor and an acceptor. Core ionizations of these form two intersecting core-ionized states, the vibronic coupling between which along the OH stretching mode partially delocalizes the core hole, resulting in a hopping of the core hole from one site to another. This, in turn, affects the dynamics of the proton transfer in the core-ionized state. The quantum dynamical simulations of X-ray photoelectron spectra of glyoxalmonoxime driven by strong IR pulses demonstrate the general applicability of the technique for studies of intramolecular proton transfer in systems with vibronic coupling.

Place, publisher, year, edition, pages
2006. Vol. 110, no 47, 12805-12813 p.
Keyword [en]
Approximation theory; Ionization; Isomers; Molecular vibrations; Protons; Quantum theory; X ray analysis
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-5654DOI: 10.1021/jp065036dISI: 000242298800012Scopus ID: 2-s2.0-33846115235OAI: oai:DiVA.org:kth-5654DiVA: diva2:10092
Note

Uppdaterad från manuskript till artikel: 20100825 QC 20100825

Available from: 2006-05-05 Created: 2006-05-05 Last updated: 2017-12-14Bibliographically approved
In thesis
1. X-ray Spectroscopy of Molecules Driven by Strong IR Fields
Open this publication in new window or tab >>X-ray Spectroscopy of Molecules Driven by Strong IR Fields
2006 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

The current thesis deals with one important branch of the physics of ultrafast processes, namely modeling of femtosecond nuclear dynamics. We suggest a new type of time resolved spectroscopy, the phase sensitive infrared-x-ray pump probe spectroscopy, which combines rich opportunities of IR laser techniques in quantum control of molecular systems with the site selectivity of x-rays. We have developed and applied a dynamical theory of x-ray pump-probe spectroscopy to study different molecular systems. Special attention is paid to design of the wave packets of desirable shape and spectral composition. Such a quantum control of the nuclear wave packet enables the study of molecular properties in regions that are unavailable by standard x-ray spectroscopies. The IR - x-ray pump probe spectroscopy is nicely suited to perform mapping of wave packet trajectories, to study revival phenomena, femtosecond chemical dynamics, and proton transfer, to mention a few examples.

Our simulations show that the phase of the infrared pulse strongly influences the trajectory of the nuclear wave packet, and hence, the x-ray spectrum. Such a dependence is caused by the transfer of the phase of the IR field to the wave packet through the interference of the one (x-ray) and two-photon (IR + x-ray) excitation channels. The time resolved x-ray spectra are sensitive to the shape, duration and delay time between the pulses. The phase of the IR pulse influences the molecular dynamics also when the Rabi period becomes comparable with the period of vibrations, breaking down the rotating wave approximation. We predict a phase memory effect which is a promising technique in studies of chemical dynamics on different time scales. It is shown that the final state interaction with the pump affects the probe spectrum when the pump and probe pulses overlap.

In a further step, we explore the electronic recoil effect in x-ray photoelectron spectroscopy, which has recently attracted attention of experimentalists due to its sensitivity to intramolecular interaction. We show that an IR field enhances the manifestation of the recoil effect through the formation of extensive vibrational wave packets. The theory of x-ray Raman scattering from molecules with strong spin-orbit coupling accompanied by electron-hole interaction is developed and applied to simulations of resonant x-ray Raman scattering of the HCl molecule. Special attention is paid to the theoretical methodologies to reduce the computational cost of our wave packet codes.

Place, publisher, year, edition, pages
Stockholm: KTH, 2006. ix, 53 p.
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-3937 (URN)91-7178-277-X (ISBN)
Public defence
2006-05-19, Sal FR4, AlbaNova Universitetscentrum, Roglagstullsbacken 21, Stochholm, 10:00
Opponent
Supervisors
Note
QC 20100825Available from: 2006-05-05 Created: 2006-05-05 Last updated: 2011-11-23Bibliographically approved
2. 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
Opponent
Supervisors
Note

QC 20170222

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

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