Mechanisms of Franck–Condon breakdown over a broad energy range in the valence photoionization of N2 and CO

López-Domínguez, Jesús A.; Hardy, D.; Das, Aloke; Poliakoff, E. D.; Aguilar, A.; Lucchese, Robert R.

doi:10.1016/j.elspec.2012.06.016

Cited by 13 publications

(9 citation statements)

References 43 publications

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“…[3][4][5] Less common have been theoretically backed investigations of explicit vibrational influences exerted on the photoelectron angular distributions (PADs). The influence of full Herzberg-Teller type vibronic interaction has been discussed [6] in this context, but more typically approaches based upon treating the parametric dependence of the electronic matrix element upon nuclear geometry have provided understanding.…”

Section: Introductionmentioning

confidence: 99%

Identifying and Understanding Strong Vibronic Interaction Effects Observed in the Asymmetry of Chiral Molecule Photoelectron Angular Distributions

et al. 2017

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Ivan (2017) Identifying and understanding strong vibronic interaction effects observed in the asymmetry of chiral molecule photoelectron angular distributions. ChemPhysChem, 18 (5 A note on versions:The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription. AbstractElectron-ion coincidence imaging is used to study chiral asymmetry in the angular distribution of electrons emitted from randomly-oriented enantiomers of two molecules, methyloxirane and trifluoromethyloxirane, upon ionization by circularly polarized VUV synchrotron radiation. Vibrationally-resolved photoelectron circular dichroism (PECD) measurements of the outermost orbital ionization reveal unanticipated large fluctuations in the magnitude of the forward-backward electron scattering asymmetry, including even a complete reversal of direction. Identification and assignment of the vibrational excitations is supported by Franck-Condon simulations of the photoelectron spectra. A previously proposed quasi-diatomic model for PECD is developed and extended to treat polyatomic systems. The parametric dependence of the electronic dipole matrix elements on nuclear geometry is evaluated in the adiabatic approximation, and provokes vibrational level dependent shifts in amplitude and phase, to which the chiral photoelectron angular distributions are especially sensitive. It is shown that single quantum excitation of those vibrational modes which experience only a relatively small displacement of the ion equilibrium geometry along the normal coordinate, and which are then only weakly excited in the Franck-Condon limit, can be accompanied by big shifts in scattering phase; hence the observed big fluctuations in PECD asymmetry for such modes.

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Section: Introductionmentioning

confidence: 99%

Identifying and Understanding Strong Vibronic Interaction Effects Observed in the Asymmetry of Chiral Molecule Photoelectron Angular Distributions

et al. 2017

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“…The appearance of this second maximum is due to a phenomenon called shape resonance [43] . These shape resonances for CO molecules are clearly identified in the photo-ionisation spectra of states X [44,45] , A [44] and B [45−47] . The peaks associated with shape resonances are located near 23.5 eV, 22 eV and 32 eV for states X, A and B, respectively, and they are well reproduced in our calculations.…”

Section: Resultsmentioning

confidence: 99%

Calculation of Photo-Ionisation Cross Sections and Radiative Recombination Rate Coefficients for CO and CO⁺Molecules

Dhouioui¹,

Teulet²,

Cressault³

et al. 2014

Plasma Sci. Technol.

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A method based upon the weighted total cross section (WTCS) theory is proposed to calculate the photo-ionisation cross sections and the radiative recombination rate coefficients between the fundamental level of CO and the main electronic states of its corresponding ion. Total photo-ionisation cross sections and radiative recombination rate coefficients are determined from the calculation of elementary vibrational photo-ionisation cross sections. Transitions between CO + (X, A and B) and CO(X) are considered. Total photo-ionisation cross sections and recombination coefficients are computed in the temperature interval 500-15000 K.

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“…is the vibrational wavepacket on the PEC of the Q 1 state, which we evaluate using equation (14). Δω F ( )accounts for the spectral components of the short laser pulse Δω…”

Section: Analytical Solution For a Vibrational Wavepacket On The Intementioning

confidence: 99%

“…Measurements of vibrationally resolved spectra in molecular hydrogen have recently been performed by means of photoelectron [11] and electron-scattering [12] spectroscopy. Measurements are also available for more complex diatomic and triatomic molecules (see, e.g., [13][14][15][16] and references therein). Although the experimental efforts were not aimed at a detailed study of the decay of doubly excited states, the published spectra do show resonant features (which, however, have mostly been ignored so far).…”

Section: Introductionmentioning

confidence: 99%

Signatures of attosecond electronic–nuclear dynamics in the one-photon ionization of molecular hydrogen: analytical model versusab initiocalculations

et al. 2015

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We present an analytical model based on the time-dependent WKB approximation to reproduce the photoionization spectra of an H 2 molecule in the autoionization region. We explore the nondissociative channel, which is the major contribution after one-photon absorption, and we focus on the features arising in the energy differential spectra due to the interference between the direct and the autoionization pathways. These features depend on both the timescale of the electronic decay of the autoionizing state and the time evolution of the vibrational wavepacket created in this state. With full ab initio calculations and with a one-dimensional approach that only takes into account the nuclear wavepacket associated to the few relevant electronic states we compare the ground state, the autoionizing state, and the background continuum electronic states. Finally, we illustrate how these features transform from molecular-like to atomic-like by increasing the mass of the system, thus making the electronic decay time shorter than the nuclear wavepacket motion associated with the resonant state. In other words, autoionization then occurs faster than the molecular dissociation into neutrals.

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Mechanisms of Franck–Condon breakdown over a broad energy range in the valence photoionization of N2 and CO

Cited by 13 publications

References 43 publications

Identifying and Understanding Strong Vibronic Interaction Effects Observed in the Asymmetry of Chiral Molecule Photoelectron Angular Distributions

Identifying and Understanding Strong Vibronic Interaction Effects Observed in the Asymmetry of Chiral Molecule Photoelectron Angular Distributions

Calculation of Photo-Ionisation Cross Sections and Radiative Recombination Rate Coefficients for CO and CO⁺Molecules

Signatures of attosecond electronic–nuclear dynamics in the one-photon ionization of molecular hydrogen: analytical model versusab initiocalculations

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Mechanisms of Franck–Condon breakdown over a broad energy range in the valence photoionization of N2 and CO

Cited by 13 publications

References 43 publications

Identifying and Understanding Strong Vibronic Interaction Effects Observed in the Asymmetry of Chiral Molecule Photoelectron Angular Distributions

Identifying and Understanding Strong Vibronic Interaction Effects Observed in the Asymmetry of Chiral Molecule Photoelectron Angular Distributions

Calculation of Photo-Ionisation Cross Sections and Radiative Recombination Rate Coefficients for CO and CO+Molecules

Signatures of attosecond electronic–nuclear dynamics in the one-photon ionization of molecular hydrogen: analytical model versusab initiocalculations

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Product

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Calculation of Photo-Ionisation Cross Sections and Radiative Recombination Rate Coefficients for CO and CO⁺Molecules