Hexamethylcyclopentadiene: time-resolved photoelectron spectroscopy and ab initio multiple spawning simulations

Wolf, Thomas; Kuhlman, Thomas Scheby; Schalk, Oliver; Martı́nez, Todd J.; Møller, Klaus Braagaard; Stolow, Albert; Unterreiner, Andreas‐Neil

doi:10.1039/c4cp00977k

Cited by 35 publications

(47 citation statements)

References 60 publications

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“…30 In contrast to previous work, TDDFT-SH shows that the reaction dynamics take place on a single excited state only, which is similar to previous findings on cyclopenta-1,3-diene where another method (MS-MR-CASPT2) was used. 47,48 After excitation, the molecule stretches the For the hexatriene ground state, the simulations allowed us to follow the dynamics for 5 ps and we found that, after the Woodward-Hoffmann allowed conrotatory ring-opening, the tZt conformer is formed within 200 fs while the other conformers are formed afterwards, in slight disagreement with earlier work based on Ehrenfest dynamics simulations. 15 Therefore, more work will be necessary to disentangle the ground state rearrangements on a 100 femtosecond time scale.…”

Section: Discussionsupporting

confidence: 40%

“…While the involvement of this state in the photodynamical trajectories seems to be well established in the case of open chained molecules, 71, 72 this is not necessarily so for cyclic dienes as inferred before for the case of CPD. 47,48 For CHD, we also find evidence for just one excited state in the reaction path, both through our photoelectron spectra and our ab initio calculations. Along the reaction coordinate, the character of the excited states changes, which was observed in earlier studies of CHD 30,73 but is also known from other small dienes that exhibit large amplitude motions such as butadiene 72 or CPD.…”

Section: Comparison With Literaturementioning

confidence: 65%

“…According to the analysis of the CPD data by Wolf et al, 48 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 is characterized by the extra maximum at 180 fs (see below for an explanation) which is absent in the spectrum of the successful trajectories. The appearance of this feature in the TRPES data shows, indeed, that some of the molecules do not undergo ring opening.…”

Section: Computational Resultsmentioning

confidence: 99%

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Cyclohexadiene Revisited: A Time-Resolved Photoelectron Spectroscopy and ab Initio Study

et al. 2016

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We have reinvestigated the excited state dynamics of cyclohexa-1,3-diene (CHD) with time-resolved photoelectron spectroscopy and fewest switches surface hopping molecular dynamics based on linear response time-dependent density functional theory after excitation to the lowest lying ππ* (1B) state. The combination of both theory and experiment revealed several new results: First, the dynamics progress on one single excited state surface. After an incubation time of 35 ± 10 fs on the excited state, the dynamics proceed to the ground state in an additional 60 ± 10 fs, either via a conrotatory ring-opening to hexatriene or back to the CHD ground state. Moreover, ring-opening predominantly occurs when the wavepacket crosses the region of strong nonadiabatic coupling with a positive velocity in the bond alternation coordinate. After 100 fs, trajectories remaining in the excited state must return to the CHD ground state. This extra time delay induces a revival of the photoelectron signal and is an experimental confirmation of the previously formulated model of two parallel reaction channels with distinct time constants. Finally, our simulations suggest that after the initially formed cis-Z-cis HT rotamer the trans-Z-trans isomer is formed, before the thermodynamical equilibrium of three possible rotamers is reached after 1 ps.

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Section: Discussionsupporting

confidence: 40%

Section: Comparison With Literaturementioning

confidence: 65%

Section: Computational Resultsmentioning

confidence: 99%

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Cyclohexadiene Revisited: A Time-Resolved Photoelectron Spectroscopy and ab Initio Study

et al. 2016

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“…This shift is a sign of large amplitude motion experienced by photoexcited molecule and caused by both the rise of the vertical ionization potential along the large amplitude deformation coordinates and the conversion of potential energy into kinetic energy of the molecule. 48,49 In the present case, treating time zero as an additional fitting parameter yields a shift by 14 ± 6 fs. The decay-associated spectra (DAS) and the visualization of time zero fitting parameters are plotted in the Supporting Information ( Figure SI2).…”

Section: Experimental and Theoretical Methodsmentioning

confidence: 99%

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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“…Ionization is also the first step in the high-harmonic generation of XUV and soft X-ray attosecond pulses, [8][9][10][11] and has been used as a tool for imaging molecular orbitals, [12][13][14][15] since the angular distribution of the ionization yield reflects the shape of the original molecular orbital. 16 A broadband superposition of valence excited states of the cation is prepared and monitored.…”

Section: Introductionmentioning

confidence: 99%

Three-dimensional attosecond resonant stimulated X-ray Raman spectroscopy of electronic excitations in core-ionized glycine

Zhang

Biggs

Hua

et al. 2014

Phys. Chem. Chem. Phys.

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We investigate computationally the valence electronic excitations of the amino acid glycine prepared by a sudden nitrogen core ionization induced by an attosecond X-ray pump pulse. The created superposition of cationic excited states is probed by two-dimensional transient X-ray absorption and by three dimensional attosecond stimulated X-ray Raman signals. The latter, generated by applying a second broadband X-ray pulse combined with a narrowband pulse tuned to the carbon K-edge, reveal the complex coupling between valence and core-excited manifolds of the cation.

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Hexamethylcyclopentadiene: time-resolved photoelectron spectroscopy and ab initio multiple spawning simulations

Abstract: Time-resolved photoelectron spectroscopy and ab initio multiple spawning dynamical simulations of hexamethylcyclopentadiene reveal wavepacket evolution in a distinct degree of freedom.

Cited by 35 publications

References 60 publications

Cyclohexadiene Revisited: A Time-Resolved Photoelectron Spectroscopy and ab Initio Study

Cyclohexadiene Revisited: A Time-Resolved Photoelectron Spectroscopy and ab Initio Study

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

Three-dimensional attosecond resonant stimulated X-ray Raman spectroscopy of electronic excitations in core-ionized glycine

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