Vibrational state dependence of β and D asymmetry parameters: The case of the highest occupied molecular orbital photoelectron spectrum of methyl-oxirane

Contini, G.; Zema, N.; Turchini, S.; Catone, Daniele; Prosperi, T.; Carravetta, Vincenzo; Bolognesi, P.; Avaldi, L.; Feyer, Vitaliy

doi:10.1063/1.2779324

Cited by 29 publications

(29 citation statements)

References 33 publications

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“…So far, all published PECD studies have been vibrationally unresolved, except for a study of methyloxirane22 performed at the single-photon energy of 22 eV, that is, about 12 eV above the ionization potential (IP), and that shows some weak modulations of the dichroism seemingly correlated with the partially resolved vibrational envelope of the highest occupied molecular orbital (HOMO). We decided to reinvestigate this showcase chiral molecular system but with much slower photoelectrons, that is, in the first eV above the IP where we expect PECD to be able to provide rich information on vibrational dynamics and for which our electron imaging technique is very efficient and capable of a high absolute energy resolution.…”

Section: Resultsmentioning

confidence: 99%

Vibrationally induced inversion of photoelectron forward-backward asymmetry in chiral molecule photoionization by circularly polarized light

et al. 2013

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Electron–nuclei coupling accompanying excitation and relaxation processes is a fascinating phenomenon in molecular dynamics. A striking and unexpected example of such coupling is presented here in the context of photoelectron circular dichroism measurements on randomly oriented, chiral methyloxirane molecules, unaffected by any continuum resonance. Here, we report that the forward-backward asymmetry in the electron angular distribution, with respect to the photon axis, which is associated with photoelectron circular dichroism can surprisingly reverse direction according to the ion vibrational mode excited. This vibrational dependence represents a clear breakdown of the usual Franck–Condon assumption, ascribed to the enhanced sensitivity of photoelectron circular dichroism (compared with other observables like cross-sections or the conventional anisotropy parameter-β) to the scattering phase off the chiral molecular potential, inducing a dependence on the nuclear geometry sampled in the photoionization process. Important consequences for the interpretation of such dichroism measurements within analytical contexts are discussed.

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Section: Resultsmentioning

confidence: 99%

Vibrationally induced inversion of photoelectron forward-backward asymmetry in chiral molecule photoionization by circularly polarized light

et al. 2013

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“…Successively the same effect was measured in the core levels [8] and in valence-band vibrationally resolved photoelectron spectroscopy. [9] The strong intensity of the dipole dissymmetry is particularly promising for exploitation in gas-phase experiments, in which it is possible to take advantage of the highly developed experimental methods of photoelectron spectroscopy. The first comparison between calculated and experimental valence dichroism was performed on the valence bands of methyloxirane.…”

Section: à3mentioning

confidence: 99%

Conformational Effects in Photoelectron Circular Dichroism of Alaninol

et al. 2009

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A photoelectron circular dichroism (CD) study of the valence states of 2-amino-1-propanol (alaninol) in the gas phase is presented. The aim of the investigation is to reveal conformer population effects in the valence-state photoelectron spectrum. The experimental dispersion of the dichroic D parameter of valence states as a function of the photon excitation energy is compared with its theoretical value calculated by employing a multicentric basis set of B-spline functions and a Kohn-Sham Hamiltonian. The theoretical values are in very good agreement with the experimental data when the conformer population distribution is taken into account. Moreover, thanks to a comparison between experiment and theory, a clear assignment of the molecular orbital character and conformer geometry is given to the features of the photoelectron spectrum. This work indicates in a detailed experimental analysis that CD in photoelectron spectroscopy is an effective technique to disentangle the conformer assignment in photoelectron spectra.

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“…CH 3 ) produces significant changes in the sign and/or magnitude of the circular dichroism. [34][35][36] In conclusion, we have investigated, by using circular dichroism in the angle distribution of valence photoelectrons, the chiral electronic features of the extended 2D domain of chiral selfassembled molecular structure originating from the adsorption of L-and D-alaninol on Cu(100).…”

Section: -25mentioning

confidence: 99%

Transfer of chirality from adsorbed chiral molecules to the substrate highlighted by circular dichroism in angle-resolved valence photoelectron spectroscopy

et al. 2012

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The study of self-assembled chiral molecules on achiral metallic surfaces is mostly focused on the determination of the geometry of adsorbates and the related electronic structure. The aim of this paper is to provide direct information on the chirality character of the system and on the chirality transfer from molecules to the substrate by means of circular dichroism in the angular distribution of valence photoelectrons for extended domain of chiral self-assembled molecular structure, formed by alaninol adsorbed on Cu(100). We show that the presence of molecular chiral domains induces chiral electronic states in the interaction with the substrate and locally transfers chiral character to the underneath metal atoms participating in the adsorption process. Identification of chirality in the adsorption footprint represents an important aspect for controlling and tuning the functionality of the molecular-metal interfaces.

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Vibrational state dependence of β and D asymmetry parameters: The case of the highest occupied molecular orbital photoelectron spectrum of methyl-oxirane

Cited by 29 publications

References 33 publications

Vibrationally induced inversion of photoelectron forward-backward asymmetry in chiral molecule photoionization by circularly polarized light

Vibrationally induced inversion of photoelectron forward-backward asymmetry in chiral molecule photoionization by circularly polarized light

Conformational Effects in Photoelectron Circular Dichroism of Alaninol

Transfer of chirality from adsorbed chiral molecules to the substrate highlighted by circular dichroism in angle-resolved valence photoelectron spectroscopy

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