Rovibronic photoionization dynamics of asymmetric-top molecules

Willitsch, Stefan; Merkt, Frédéric

doi:10.1016/j.ijms.2005.06.004

Cited by 59 publications

(67 citation statements)

References 103 publications

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“…The orbital ionization model, as applied so far in polyatomic molecules, 56 has been restricted to transitions between neutral and ionic states both described by Hund's-case-(b)-type angular-momentum coupling and has two main deficiencies in the present case. First, it disregards effects resulting from the spin-orbit coupling and does not, therefore, account for the projection + of the electron spin in theX +2 E cation.…”

Section: A Photoionization Selection Rulesmentioning

confidence: 99%

Photoelectron spectroscopic study of the E⊗e Jahn–Teller effect in the presence of a tunable spin–orbit interaction. I. Photoionization dynamics of methyl iodide and rotational fine structure of CH3I+ and CD3I+

Grütter

Michaud

Merkt

2011

The Journal of Chemical Physics

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The high-resolution single-photon pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the \documentclass[12pt]{minimal}\begin{document}$\tilde{\rm {X}}^+$\end{document}X̃+ 2\documentclass[12pt]{minimal}\begin{document}$\rm {E_{3/2}}\leftarrow \tilde{\rm {X}}\, ^1{\rm A}_1$\end{document}E3/2←X̃1A1 transition of CH3I and CD3I have been recorded. The spectral resolution of better than 0.15 cm−1 enabled the observation of the rotational structure. CH3I+ and CD3I+ are subject to a weak \documentclass[12pt]{minimal}\begin{document}$\rm {E}\otimes \rm {e}$\end{document}E⊗e Jahn–Teller effect and strong spin–orbit coupling. The treatment of the rovibronic structure of the photoelectron spectra in the corresponding spin double group, \documentclass[12pt]{minimal}\begin{document}$\rm {C_{3v}^2(M)}$\end{document}C3v2(M), including the effects of the spin–orbit interaction and the vibrational angular momentum, allowed the reproduction of the experimentally observed transitions with spectroscopic accuracy. The relevant spin–orbit and linear Jahn–Teller coupling parameters of the \documentclass[12pt]{minimal}\begin{document}$\tilde{\rm {X}}^+$\end{document}X̃+ ground state were derived from the analysis of the spectra of the two isotopomers, and improved values were obtained for the adiabatic ionization energies [\documentclass[12pt]{minimal}\begin{document}${E_{\rm {I}}(\rm {CH}_3\rm {I})}/hc =76931.35(20)$\end{document}EI( CH 3I)/hc=76931.35(20) cm−1 and \documentclass[12pt]{minimal}\begin{document}${E_{\rm {I}}(\rm {CD}_3\rm {I})}/hc=76957.40(20)$\end{document}EI( CD 3I)/hc=76957.40(20) cm−1] and the rotational constants of the cations. Rovibronic photoionization selection rules were derived for transitions connecting neutral states following Hund's-case-(b)-type angular momentum coupling and ionic states following Hund's-case-(a)-type coupling. The selection rules, expressed in terms of the angular momentum projection quantum number P, account for all observed transitions and provide an explanation for the nonobservation of several rotational sub-bands in the mass-analyzed threshold-ionization spectra of \documentclass[12pt]{minimal}\begin{document}$\rm {CH}_3\rm {I}$\end{document} CH 3I and \documentclass[12pt]{minimal}\begin{document}$\rm {CD}_3\rm {I}$\end{document} CD 3I reported recently by Lee et al. [J. Chem. Phys. 128, 044310 (2008)].

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Section: A Photoionization Selection Rulesmentioning

confidence: 99%

Photoelectron spectroscopic study of the E⊗e Jahn–Teller effect in the presence of a tunable spin–orbit interaction. I. Photoionization dynamics of methyl iodide and rotational fine structure of CH3I+ and CD3I+

Grütter

Michaud

Merkt

2011

The Journal of Chemical Physics

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“…The orbital ionization model described in detail in Ref. 33 was used to calculate the rotational intensity distributions of the spectra. In the orbital ionization model, the angular momentum of the photon is assumed to be fully absorbed by the outgoing photoelectron, creating a hole of the same angular momentum composition as the molecular orbital out of which ionization occurs.…”

Section: -5mentioning

confidence: 99%

“…͑7͒ of Ref. 33, only contributions to the single-center expansion of p and d angular momentum character have been taken into account with relative weights of 0.6 and 1.0, respectively, which implies the selection rules ͉⌬N͉ = ͉N + − NЉ͉ Յ 2 and ⌬K a = K a + − KЉ = Ϯ 1. The simulated spectra presented in Figs.…”

Section: -5mentioning

confidence: 99%

Rotationally resolved photoelectron spectroscopic study of the Jahn–Teller effect in allene

Schulenburg

Merkt

2009

The Journal of Chemical Physics

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The pulsed-field-ionization zero-kinetic-energy photoelectron spectra of allene (C3H4) and perdeuterated allene have been recorded from the first adiabatic ionization energy up to 2200 cm−1 of internal energy in the cations at a resolution sufficient to observe the full rotational structure. The intensity distributions in the spectra are dominated by vibrational progressions in the torsional mode, which were analyzed in the realm of a two-dimensional model of the E⊗(b1⊕b2) Jahn–Teller effect in the allene cation [C. Woywod and W. Domcke, Chem. Phys. 162, 349 (1992)]. Whereas the rotational structure of the transitions to the lowest torsional levels (00 and 41) are regular and can be qualitatively analyzed in terms of a simple orbital ionization model, the rotational structure of the spectra of the 42 and 43 levels are strongly perturbed. The photoelectron spectrum of C3H4 also reveals several weak vibrational bands in the immediate vicinity of these levels that are indicative of (ro)vibronic perturbations. A slight broadening of the transitions to the 41 levels compared to that of the vibronic ground state and the increase of the number of sharp features in the rotational structure of the spectrum of the 42 level point at the importance of large-amplitude motions not considered in previous treatments of the Jahn–Teller effect in the allene cation.

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“…17 and the orbital ionization model described in Ref. 18 are displayed for comparison below the experimental spectrum in Figure 2 and between 4 the two experimental spectra in Figure 3.…”

Section: Resultsmentioning

confidence: 99%

The Rotational Structure of the Origin Band of the Pulsed-Field-Ionization, Zero-Kinetic-Energy Photoelectron Spectra of Propene-h₆ and Propene-d₆

2010

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The pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the origin band of the X ˜+ 2 A′′ r X 1A′ transition of propene (C 3 H 6 ) and perdeuterated propene (C 3 D 6 ) have been recorded at high resolution, allowing for the partial resolution of the rotational structure. The analysis of the spectra in the realm of the orbital ionization model for rigid-rotor asymmetric-top molecules enabled the determination of the adiabatic ionization energy of propene and the rotational constants of C 3 H 6 + and C 3 D 6 +. The tunneling splittings resulting from the hindered rotation of the methyl group could not be resolved, and the analysis was therefore carried out in the C s molecular symmetry group. Angular momentum contributions of p π , d π , and d δ character were included in the single-center expansion describing the molecular orbital out of which ionization occurs, leading to the selection rules |∆N| ) |N + -N′′| e 2 and ∆K a ) K a + -K a ′′ ) (1, (2 and to photoelectron partial waves with angular momentum quantum number up to l ) 3. The observation of a strong spectral feature associated with ∆K a ) 0 indicates the importance of vibronic interactions. † Part of the "Klaus Mu ¨ller-Dethlefs Festschrift".

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Rovibronic photoionization dynamics of asymmetric-top molecules

Cited by 59 publications

References 103 publications

Photoelectron spectroscopic study of the E⊗e Jahn–Teller effect in the presence of a tunable spin–orbit interaction. I. Photoionization dynamics of methyl iodide and rotational fine structure of CH3I+ and CD3I+

Photoelectron spectroscopic study of the E⊗e Jahn–Teller effect in the presence of a tunable spin–orbit interaction. I. Photoionization dynamics of methyl iodide and rotational fine structure of CH3I+ and CD3I+

Rotationally resolved photoelectron spectroscopic study of the Jahn–Teller effect in allene

The Rotational Structure of the Origin Band of the Pulsed-Field-Ionization, Zero-Kinetic-Energy Photoelectron Spectra of Propene-h₆ and Propene-d₆

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Rovibronic photoionization dynamics of asymmetric-top molecules

Cited by 59 publications

References 103 publications

Photoelectron spectroscopic study of the E⊗e Jahn–Teller effect in the presence of a tunable spin–orbit interaction. I. Photoionization dynamics of methyl iodide and rotational fine structure of CH3I+ and CD3I+

Photoelectron spectroscopic study of the E⊗e Jahn–Teller effect in the presence of a tunable spin–orbit interaction. I. Photoionization dynamics of methyl iodide and rotational fine structure of CH3I+ and CD3I+

Rotationally resolved photoelectron spectroscopic study of the Jahn–Teller effect in allene

The Rotational Structure of the Origin Band of the Pulsed-Field-Ionization, Zero-Kinetic-Energy Photoelectron Spectra of Propene-h6 and Propene-d6

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The Rotational Structure of the Origin Band of the Pulsed-Field-Ionization, Zero-Kinetic-Energy Photoelectron Spectra of Propene-h₆ and Propene-d₆