Femtosecond Time-Resolved Photoelectron Spectroscopy of Polyatomic Molecules

Stolow, Albert

doi:10.1146/annurev.physchem.54.011002.103809

Cited by 265 publications

(202 citation statements)

References 89 publications

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“…[7][8][9] We attempt to rationalize the different observed dynamical time scales between the molecules using high-level theoretical calculations to analyze the structures and energies of the ground and important excited states. In addition, we map the topographies of the conical intersections relevant to the dynamics that we observe.…”

Section: Introductionmentioning

confidence: 99%

Substituent Effects on Dynamics at Conical Intersections: α,β-Enones

et al. 2007

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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. June 14, 2007; In Final Form: August 21, 2007 Femtosecond time-resolved photoelectron spectroscopy and high-level theoretical calculations were used to study the effects of methyl substitution on the electronic dynamics of the R, -enones acrolein (2-propenal), crotonaldehyde (2-butenal), methylvinylketone (3-buten-2-one), and methacrolein (2-methyl-2-propenal) following excitation to the S 2 (ππ*) state at 209 and 200 nm. We determine that following excitation the molecules move rapidly away from the Franck-Condon region, reaching a conical intersection promoting relaxation to the S 1 (nπ*) state. Once on the S 1 surface, the trajectories access another conical intersection, leading them to the ground state. Only small variations between molecules are seen in their S 2 decay times. However, the position of methyl group substitution greatly affects the relaxation rate from the S 1 surface and the branching ratios to the products. Ab initio calculations used to compare the geometries, energies, and topographies of the S 1 /S 0 conical intersections of the molecules are not able to satisfactorily explain the variations in relaxation behavior. We propose that the S 1 lifetime differences are caused by specific dynamical factors that affect the efficiency of passage through the S 1 /S 0 conical intersection.

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Section: Introductionmentioning

confidence: 99%

Substituent Effects on Dynamics at Conical Intersections: α,β-Enones

et al. 2007

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“…In this, the pump pulse should be in the UV domain and no longer than a few femtoseconds (not to trigger the nuclear motion), while the probe pulse should be even shorter in order to observe the electronic motion with high-enough time resolution. The method of choice would thus be time-resolved photoelectron spectroscopy [24][25][26][27][28][29][30] using an attosecond XUV probe pulse.…”

Section: Context and Objectivesmentioning

confidence: 99%

Monitoring the Birth of an Electronic Wavepacket in a Molecule with Attosecond Time-Resolved Photoelectron Spectroscopy

et al. 2014

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“…There are a variety of experimental techniques for probing molecular dynamics, whose utility can vary from one polyatomic molecule to another one [1][2][3][4] . Among the most commonly used pump-probe signals, we can highlight photoelectron energy 5 and angular distributions (PAD) 6 , electron-ion coincidence in the perturbative regime 7,8 that can provide molecular frame-PAD 3,9 , or in the nonperturbative regime like Coulomb explosion 10 or above threshold ionization 11 . All these detections are based on collecting charged species.…”

Section: Introductionmentioning

confidence: 99%

High-harmonic transient grating spectroscopy of NO2 electronic relaxation

Ruf

Handschin

Ferré

et al. 2012

The Journal of Chemical Physics

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We study theoretically and experimentally the electronic relaxation of NO 2 molecules excited by absorption of one ∼ 400 nm pump photon. Semi-classical simulations based on trajectory surface hopping calculations are performed. They predict fast oscillations of the electronic character around the intersection of the ground and first excited diabatic states. An experiment based on high-order harmonic transient grating spectroscopy reveals dynamics occuring on the same timescale. A systematic study of the detected transient is conducted to investigate the possible influence of the pump intensity, pump wavelength, and rotational temperature of the molecules. The quantitative agreement between measured and predicted dynamics shows that, in NO 2 , high harmonic transient grating spectroscopy encodes vibrational dynamics underlying the electronic relaxation.

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Femtosecond Time-Resolved Photoelectron Spectroscopy of Polyatomic Molecules

Cited by 265 publications

References 89 publications

Substituent Effects on Dynamics at Conical Intersections: α,β-Enones

Substituent Effects on Dynamics at Conical Intersections: α,β-Enones

Monitoring the Birth of an Electronic Wavepacket in a Molecule with Attosecond Time-Resolved Photoelectron Spectroscopy

High-harmonic transient grating spectroscopy of NO2 electronic relaxation

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