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Principles of Infrared - X-ray Pump-probe Spectroscopy
KTH, School of Biotechnology (BIO), Theoretical Chemistry (closed 20110512).
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: urn:nbn:se:kth:diva-4245ISBN: 978-91-7178-508-4 OAI: oai:DiVA.org:kth-4245DiVA: diva2:11427
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
List of papers
1. Probing weak molecular orbital interactions in non-conjugated diene molecules by means of near-edge X-ray absorption spectroscopy
Open this publication in new window or tab >>Probing weak molecular orbital interactions in non-conjugated diene molecules by means of near-edge X-ray absorption spectroscopy
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2005 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 109, no 33, 7385-7395 p.Article in journal (Refereed) Published
Abstract [en]

Carbon and oxygen near-edge X-ray absorption fine structure (NEXAFS) spectra of 1,4-cyclohexadiene, p-benzoquinone, norbornadiene, norbornadienone, and cis-cis-[4,4,2]propella-3,8-diene-11,12-dione were calculated by means of Hartree-Fock and hybrid density functional theory using the static-exchange (STEX) approximation. The NEXAFS spectra are used as a probe to identify weak molecular interactions between the two non-conjugated ethylenic pi* orbitals present in these molecules. We show that the X-ray absorption spectrum of 1,4-cyclohexadiene exhibits some particular spectral structures in the discrete energy region that evidence diene through-bond orbital interaction, whereas absorption peaks are identified in the norbornadiene and norbornadienone spectra that indicate effective through-space orbital interactions. The molecular structure of the cis-cis-[4,4,2]propella-3,8-diene-11,12-dione isomer is such that the indirect through-bond or through-space diene orbital interactions are too weak to be assigned by its C1s NEXAFS spectrum.

Keyword
through-bond interactions, negative-ion states, photoelectron-spectroscopy, electron transmission, para-benzoquinone, shell excitation, anion states, pi-orbitals, spectra, 1, 4-cyclohexadiene
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-14990 (URN)10.1021/jp044757e (DOI)000231425900007 ()2-s2.0-24944579925 (Scopus ID)
External cooperation:
Note

QC 20101022 Tidigare titel: Probing through-bond and through-space interactions by means of near-edge x-ray absorption spectroscopy. A theoretical study on non-conjugated diene molecules.

Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
2. The principles of infrared-x-ray pump-probe spectroscopy. Applications on proton transfer in core-ionized water dimers
Open this publication in new window or tab >>The principles of infrared-x-ray pump-probe spectroscopy. Applications on proton transfer in core-ionized water dimers
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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
Keyword
Dimers, Ionization, Nuclear energy, Protons, Quantum theory, Watersheds
National Category
Physical Sciences
Identifiers
urn:nbn:se:kth:diva-24955 (URN)10.1063/1.1860312 (DOI)000227483300040 ()15836140 (PubMedID)2-s2.0-22944466386 (Scopus ID)
Note

QC 20101004

Available from: 2010-10-04 Created: 2010-10-04 Last updated: 2017-12-12Bibliographically approved
3. Coherent control of population of vibrational states by infrared pulses
Open this publication in new window or tab >>Coherent control of population of vibrational states by infrared pulses
(English)Manuscript (preprint) (Other academic)
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-25451 (URN)
Note
QC 20101022Available from: 2010-10-22 Created: 2010-10-22 Last updated: 2010-10-22Bibliographically approved
4. Proton transfer mediated by the vibronic coupling in oxygen core ionized states of glyoxalmonoxime studied by infrared-X-ray pump-probe spectroscopy.
Open this publication in new window or tab >>Proton transfer mediated by the vibronic coupling in oxygen core ionized states of glyoxalmonoxime studied by infrared-X-ray pump-probe spectroscopy.
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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.

Keyword
Approximation theory; Ionization; Isomers; Molecular vibrations; Protons; Quantum theory; X ray analysis
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-5654 (URN)10.1021/jp065036d (DOI)000242298800012 ()2-s2.0-33846115235 (Scopus ID)
External cooperation:
Note

Uppdaterad från manuskript till artikel: 20100825 QC 20100825

Available from: 2006-05-05 Created: 2006-05-05 Last updated: 2017-12-14Bibliographically approved
5. Infrared–x-ray pump-probe spectroscopy of the NO molecule
Open this publication in new window or tab >>Infrared–x-ray pump-probe spectroscopy of the NO molecule
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2005 (English)In: Physical Review A. Atomic, Molecular, and Optical Physics, ISSN 1050-2947, E-ISSN 1094-1622, Vol. 72, no 1, 012714Article in journal (Refereed) Published
Abstract [en]

Two color infrared-x-ray pump-probe spectroscopy of the NO molecule is studied theoretically and numerically in order to obtain a deeper insight of the underlying physics and of the potential of this suggested technology. From the theoretical investigation a number of conclusions could be drawn: It is found that the phase of the infrared field strongly influences the trajectory of the nuclear wave packet, and hence, the x-ray spectrum. The trajectory experiences fast oscillations with the vibrational frequency with a modulation due to the anharmonicity of the potential. The dependences of the x-ray spectra on the delay time, the duration, and the shape of the pulses are studied in detail. It is shown that the x-ray spectrum keep memory about the infrared phase after the pump field left the system. This memory effect is sensitive to the time of switching-off the pump field and the Rabi frequency. The phase effect takes maximum value when the duration of the x-ray pulse is one-fourth of the infrared field period, and can be enhanced by a proper control of the duration and intensity of the pump pulse. The manifestation of the phase is different for oriented and disordered molecules and depends strongly on the intensity of the pump radiation.

Keyword
synchrotron-radiation, laser, pulses, simulation, generation, dynamics, spectra, phase
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-5650 (URN)10.1103/PhysRevA.72.012714 (DOI)000230887300094 ()2-s2.0-27144550517 (Scopus ID)
Note

QC 20100825

Available from: 2006-05-05 Created: 2006-05-05 Last updated: 2017-12-14Bibliographically approved
6. Selective decomposition of water clusters by strong infrared fields: Rextification of the Lorentz force as a novel mechanism of bond breaking
Open this publication in new window or tab >>Selective decomposition of water clusters by strong infrared fields: Rextification of the Lorentz force as a novel mechanism of bond breaking
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(English)Manuscript (preprint) (Other academic)
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-25454 (URN)
Note
QC 20101022Available from: 2010-10-22 Created: 2010-10-22 Last updated: 2010-10-22Bibliographically approved

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