Photoionization-induced pi <-> H site switching dynamics in phenol(+)-Rg (Rg = Ar, Kr) dimers probed by picosecond time-resolved infrared spectroscopy
dc.contributor.author | Miyazaki, Mitsuhiko | |
dc.contributor.author | Sakata, Yuri | |
dc.contributor.author | Schütz, Markus | |
dc.contributor.author | Dopfer, Otto | |
dc.contributor.author | Fujii, Masaaki | |
dc.date.accessioned | 2017-10-24T07:15:17Z | |
dc.date.available | 2017-10-24T07:15:17Z | |
dc.date.issued | 2016 | |
dc.description | Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich. | de |
dc.description | This 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.abstract | The 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.eissn | 1463-9084 | |
dc.identifier.issn | 1463-9076 | |
dc.identifier.pmid | 27550720 | |
dc.identifier.uri | https://depositonce.tu-berlin.de/handle/11303/6896 | |
dc.identifier.uri | http://dx.doi.org/10.14279/depositonce-6235 | |
dc.language.iso | en | |
dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | |
dc.subject.ddc | 540 Chemie und zugeordnete Wissenschaften | de |
dc.title | Photoionization-induced pi <-> H site switching dynamics in phenol(+)-Rg (Rg = Ar, Kr) dimers probed by picosecond time-resolved infrared spectroscopy | en |
dc.type | Article | en |
dc.type.version | publishedVersion | en |
dcterms.bibliographicCitation.doi | 10.1039/c6cp05016f | |
dcterms.bibliographicCitation.issue | 35 | |
dcterms.bibliographicCitation.journaltitle | Physical chemistry, chemical physics | en |
dcterms.bibliographicCitation.originalpublishername | Royal Society of Chemistry | de |
dcterms.bibliographicCitation.originalpublisherplace | Cambridge | de |
dcterms.bibliographicCitation.pageend | 24754 | |
dcterms.bibliographicCitation.pagestart | 24746 | |
dcterms.bibliographicCitation.volume | 18 | |
tub.accessrights.dnb | domain | |
tub.affiliation | Fak. 2 Mathematik und Naturwissenschaften::Inst. Optik und Atomare Physik::FG Lasermolekülspektroskopie und Umweltphysik | de |
tub.affiliation.faculty | Fak. 2 Mathematik und Naturwissenschaften | de |
tub.affiliation.group | FG Lasermolekülspektroskopie und Umweltphysik | de |
tub.affiliation.institute | Inst. Optik und Atomare Physik | de |
tub.publisher.universityorinstitution | Technische Universität Berlin |
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