The origin of ultrafast proton transfer: Multidimensional wave packet motion vs. tunneling

Schriever, Christian; Lochbrunner, Stefan; Ofial, Armin R.; Riedle, Eberhard

doi:10.1016/j.cplett.2010.12.087

Cited by 59 publications

(85 citation statements)

References 29 publications

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“…Taking into account previous studies, typical time constants for intramolecular proton transfer lie on a 10 fs time scale. 53,57 Thus, the observed fast shift in the onset of the photoelectron spectrum of 14 ± 6f s( section 3.2) in the gas phase can be attributed to proton migration to the aci-nitro form of o-NP. Because the proton transfer is accompanied by rotation around the C−N bond, as mentioned above, "full" outof-plane twist of the newly formed HONO group by ∼73°and return to the ground state is supposed to occur on a longer time scale.…”

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

“…However, conclusions regarding the sequence of intramolecular nuclear motions have to be drawn with caution. Although it is likely that hydrogen atom transfer precedes torsion of HONO due to different reduced masses (excited state intramolecular proton transfers are known to proceed in <50 fs, 53,54 if they are virtually barrierless as in the present case), only detailed trajectory or wave packet calculations could give a decisive answer on actual reaction pathways. (Figure 6).…”

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

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Ultrafast Dynamics of o-Nitrophenol: An Experimental and Theoretical Study

et al. 2015

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Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://doi.org/10.1021/acs.jpca.5b04900Access and use of this website and the material on it are subject to the Terms and Conditions set forth at Ultrafast dynamics of o-nitrophenol: An experimental and theoretical study Ernst, Hanna A.; Wolf, Thomas J. A.; Schalk, Oliver; González-García, Nuria; Boguslavskiy, Andrey E.; Stolow, Albert; Olzmann, Matthias; Unterreiner, Andreas-Neil http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/droits L'accès à ce site Web et l'utilisation de son contenu sont assujettis aux conditions présentées dans le site LISEZ CES CONDITIONS ATTENTIVEMENT AVANT D'UTILISER CE SITE WEB. NRC Publications Record / Notice d'Archives des publications de CNRC:http://nparc.cisti-icist.nrc-cnrc.gc.ca/eng/view/object/?id=ce83ef5b-a095-4e1f-85dd-e4e329f4a190 http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/voir/objet/?id=ce83ef5b-a095-4e1f-85dd-e4e329f4a190 ABSTRACT: The photolysis of o-nitrophenol (o-NP), a typical push−pull molecule, is of current interest in atmospheric chemistry as a possible source of nitrous acid (HONO). To characterize the largely unknown photolysis mechanism, the dynamics of the lowest lying excited singlet state (S 1 )o fo-NP was investigated by means of femtosecond transient absorption spectroscopy in solution, time-resolved photoelectron spectroscopy (TRPES) in the gas phase and quantum chemical calculations. Evidence of the unstable aci-nitro isomer is provided both in the liquid and in the gas phase. Our results indicate that the S 1 state displays strong charge transfer character, which triggers excited state proton transfer from the OH to the NO 2 group as evidenced by a temporal shift of 20 fs of the onset of the photoelectron spectrum. The proton transfer itself is found to be coupled to an out-ofplane rotation of the newly formed HONO group, finally leading to a conical intersection between S 1 and the ground state S 0 . In solution, return to S 0 within 0.2−0.3 ps was monitored by stimulated emission. As a competitive relaxation channel, ultrafast intersystem cro...

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Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

Ultrafast Dynamics of o-Nitrophenol: An Experimental and Theoretical Study

et al. 2015

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“…The ESIPT reaction has also been observed for HBT in polar solvents, but the proton‐transfer kinetics do not show simple monoexponential behavior, although they do occur on a similar time scale as that observed in tetrachloroethylene . Riedle and co‐workers measured 50 fs for the ESIPT process in HBT , and the tunneling mechanism was not found to be decisive . An upper limit of 100 ps has been determined for the proton‐transfer time constant in HBI due to insufficient time resolution .…”

Section: Photophysics Of Hbxs In Solutionmentioning

confidence: 99%

Photophysical properties of hydroxyphenyl benzazoles and their applications as fluorescent probes to study local environment in DNA, protein and lipid

2016

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Fluorescence techniques have drawn increasing attention because they provide crucial information about molecular interactions in protein-ligand systems beyond that obtained by other methods. The advantage of fluorescence spectroscopy stems from the fact that the majority of molecules in biological systems do not exhibit fluorescence, making fluorescent probes useful with high sensitivity. Also, the fluorescence emission is highly sensitive to the local environment, providing a valuable tool to investigate the nature of binding sites in macromolecules. In this review, we discuss some of the important applications of a class of molecules that have been used as fluorescent probes in a variety of studies. Hydroxyphenyl benzazoles (HBXs) show distinct spectroscopic features that make them suitable probes for the study of certain biological mechanisms in DNA, protein and lipid. In particular, the complex photophysics of 2-(2'-hydroxyphenyl)benzoxazole (HBO) and the distinguished fluorescence signatures of its different tautomeric forms make this molecule a useful probe in several applications. Among these are probing the DNA local environment, study of the flexibility and specificity of protein-binding sites, and detecting the heterogeneity and ionization ability of the head groups of different lipidic phases. The spectroscopy of HBX molecules and some of their chemically modified structures is also reviewed.

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“…16 This compound is a molecular switch based on an ultrafast excited-state intramolecular proton transfer mechanism. 17 The investigated sample has a diameter of approximately 200 μm and was mounted at the focal point of the third parabolic mirror. It was excited by the second harmonic of a Ti:sapphire laser with 800 μW of femtosecond laser pulses at a central wavelength of 400 nm.…”

Section: Fluorescence Measurementsmentioning

confidence: 99%

All-reflective UV-VIS-NIR transmission and fluorescence spectrometer for μm-sized samples

et al. 2014

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We report on an optical transmission spectrometer optimized for tiny samples. The setup is based on all-reflective parabolic optics and delivers broadband operation from 215 to 1030 nm. A fiber-coupled light source is used for illumination and a fiber-coupled miniature spectrometer for detection. The diameter of the probed area is less than 200 μm for all wavelengths. We demonstrate the capability to record transmission, absorption, reflection, fluorescence and refractive indices of tiny and ultrathin sample flakes with this versatile device. The performance is validated with a solid state wavelength standard and with dye solutions.

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The origin of ultrafast proton transfer: Multidimensional wave packet motion vs. tunneling

Cited by 59 publications

References 29 publications

Ultrafast Dynamics of o-Nitrophenol: An Experimental and Theoretical Study

Ultrafast Dynamics of o-Nitrophenol: An Experimental and Theoretical Study

Photophysical properties of hydroxyphenyl benzazoles and their applications as fluorescent probes to study local environment in DNA, protein and lipid

All-reflective UV-VIS-NIR transmission and fluorescence spectrometer for μm-sized samples

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