Mass analyzed threshold ionization detected infrared spectroscopy: isomerization activity of the phenol-Ar cluster near the ionization threshold

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dc.contributor.authorMiyazaki, Mitsuhiko
dc.contributor.authorYoshikawa, Shunpei
dc.contributor.authorMichels, François
dc.contributor.authorMisawa, Kentaro
dc.contributor.authorIshiuchi, Shun-ichi
dc.contributor.authorSakai, Makoto
dc.contributor.authorDopfer, Otto
dc.contributor.authorMüller-Dethlefs, Klaus
dc.contributor.authorFujii, Masaaki
dc.date.accessioned2017-10-24T07:23:13Z
dc.date.available2017-10-24T07:23:13Z
dc.date.issued2015
dc.descriptionDieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.de
dc.descriptionThis publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.en
dc.description.abstractThe structure of the phenol-argon cluster (PhOH-Ar) in high-n Rydberg states is investigated by the newly developed technique of mass analyzed threshold ionization detected infrared (MATI-IR) spectroscopy. This method selectively measures IR spectra of molecular clusters in very high-n Rydberg states (n > 100) utilized in zero kinetic energy (ZEKE) photoelectron and MATI spectroscopy, whose ionic cores are essentially the same as the corresponding bare cation. The MATI-IR spectrum exhibits only the free OH stretching vibration (V-OH(pi)) when the pi-bound cluster of the neutral ground electronic state (S-0) is resonantly excited via the S-1 origin to Rydberg states converging to its adiabatic ionization energy level, IE0(pi). When Rydberg states converging to vibrationally excited levels of the local p-bound minimum are prepared, in addition to V-OH(pi) also the hydrogen-bonded OH stretching vibration (V-OH(H)) of the H-bonded global minimum is observed in the MATI-IR spectra, even for vibrational excitation of only 14 cm(-1) above IE0(pi). These results show that the pi -> H site switching reaction of the Ar ligand from the aromatic ring to the OH group proceeds only from vibrationally excited states in the p-bound cation core with a small barrier of less than 14 cm(-1) from IE0(pi). On the other hand, directly photoionized PhOH+-Ar shows both V-OH(H) and V-OH(pi) in the IR spectra, even when it is just ionized to IE0(pi). This result implies that the ionization-induced pi -> H site switching occurs without excess energy in the H-bound or pi-bound cations, in contrast to very high-n Rydberg states converging to levels of the pi-bound cation. The different efficiencies of the site switching for the Rydberg ion core and the bare ion and the mechanism for the pi -> H site switching are interpreted by direct ionization from the pi-bound to the H-bound structures in addition to the conventional vertical ionization and transitions to high-n Rydberg states.en
dc.identifier.eissn1463-9084
dc.identifier.issn1463-9076
dc.identifier.pmid25491162
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/6917
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-6256
dc.language.isoen
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.titleMass analyzed threshold ionization detected infrared spectroscopy: isomerization activity of the phenol-Ar cluster near the ionization thresholden
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/c4cp04584j
dcterms.bibliographicCitation.issue4
dcterms.bibliographicCitation.journaltitlePhysical chemistry, chemical physicsen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryde
dcterms.bibliographicCitation.originalpublisherplaceCambridgede
dcterms.bibliographicCitation.pageend2503
dcterms.bibliographicCitation.pagestart2494
dcterms.bibliographicCitation.volume17
tub.accessrights.dnbdomain
tub.affiliationFak. 2 Mathematik und Naturwissenschaften::Inst. Optik und Atomare Physik::FG Lasermolekülspektroskopie und Umweltphysikde
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Lasermolekülspektroskopie und Umweltphysikde
tub.affiliation.instituteInst. Optik und Atomare Physikde
tub.publisher.universityorinstitutionTechnische Universität Berlin

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