Photoionization-induced pi <-> H site switching dynamics in phenol(+)-Rg (Rg = Ar, Kr) dimers probed by picosecond time-resolved infrared spectroscopy

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dc.contributor.authorMiyazaki, Mitsuhiko
dc.contributor.authorSakata, Yuri
dc.contributor.authorSchütz, Markus
dc.contributor.authorDopfer, Otto
dc.contributor.authorFujii, Masaaki
dc.date.accessioned2017-10-24T07:15:17Z
dc.date.available2017-10-24T07:15:17Z
dc.date.issued2016
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 ionization-induced pi <-> H site switching reaction in phenol(+)-Rg (PhOH+-Rg) dimers with Rg = Ar and Kr is traced in real time by picosecond time-resolved infrared (ps-TRIR) spectroscopy. The ps-TRIR spectra show the prompt appearance of the non-vanishing free OH stretching band upon resonant photoionization of the pi-bound neutral clusters, and the delayed appearance of the hydrogen-bonded (H-bonded) OH stretching band. This result directly proves that the Rg ligand switches from the pi-bound site on the aromatic ring to the H-bonded site at the OH group by ionization. The subsequent H <-> pi back reaction converges the dimer to a pi <-> H equilibrium. This result is in sharp contrast to the single-step pi <-> H forward reaction in the PhOH+-Ar-2 trimer with 100% yield. The reaction mechanism and yield strongly depend on intracluster vibrational energy redistribution. A classical rate equation analysis for the time evolutions of the band intensities of the two vibrations results in similar estimates for the time constants of the pi <-> H forward reaction of tau(+) = 122 and 73 ps and the H <-> pi back reaction of tau_ = 155 and 188 ps for PhOH+-Ar and PhOH+-Kr, respectively. The one order of magnitude slower time constant in comparison to the PhOH+-Ar-2 trimer (tau(+) = 7 ps) is attributed to the decrease in density of states due to the absence of the second Ar in the dimer. The similar time constants for both PhOH+-Rg dimers are well rationalized by a classical interpretation based on the comparable potential energy surfaces, reaction pathways, and density of states arising from their similar intermolecular vibrational frequencies.en
dc.identifier.eissn1463-9084
dc.identifier.issn1463-9076
dc.identifier.pmid27550720
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/6896
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-6235
dc.language.isoen
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.titlePhotoionization-induced pi <-> H site switching dynamics in phenol(+)-Rg (Rg = Ar, Kr) dimers probed by picosecond time-resolved infrared spectroscopyen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/c6cp05016f
dcterms.bibliographicCitation.issue35
dcterms.bibliographicCitation.journaltitlePhysical chemistry, chemical physicsen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryde
dcterms.bibliographicCitation.originalpublisherplaceCambridgede
dcterms.bibliographicCitation.pageend24754
dcterms.bibliographicCitation.pagestart24746
dcterms.bibliographicCitation.volume18
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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