Title :

High-resolution vacuum-ultraviolet photoabsorption spectra of 1-butyne and 2-butyne

Author(s) :

Jacovella, U. [Auteur]
Holland, D. [Auteur]
Boyé-Péronne, S. [Auteur]
Laboratoire de Photophysique Moléculaire [PPM]
Gans, B. [Auteur]
de Oliveira, N. [Auteur]
Joyeux, D. [Auteur]
Archer, L. [Auteur]
Lucchese, R. [Auteur]
Xu, H. [Auteur]
Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 [IEMN]
Pratt, S. [Auteur]

Journal title :

The Journal of Chemical Physics

Pages :

034304

Publisher :

American Institute of Physics

Publication date :

2015-07-21

ISSN :

0021-9606

English keyword(s) :

Rydberg states
Oscillator strengths
Rydberg series
Vacuum ultraviolet radiation
Operator theory
Chemical elements
Photoabsorption
Fourier transform spectroscopy
Synchrotrons
Quantum chemical calculations

HAL domain(s) :

Physique [physics]

English abstract : [en]

The absolute photoabsorption cross sections of 1- and 2-butyne have been recorded at high resolution by using the vacuum-ultraviolet Fourier-Transform spectrometer at the SOLEIL Synchrotron. Both spectra show more resolved ...
Show more >The absolute photoabsorption cross sections of 1- and 2-butyne have been recorded at high resolution by using the vacuum-ultraviolet Fourier-Transform spectrometer at the SOLEIL Synchrotron. Both spectra show more resolved structure than previously observed, especially in the case of 2-butyne. In this work, we assess the potential importance of Rydberg states with higher values of orbital angular momentum, l, than are typically observed in photoabsorption experiments from ground state molecules. We show how the character of the highest occupied molecular orbitals in 1- and 2-butyne suggests the potential importance of transitions to such high-l (l = 3 and 4) Rydberg states. Furthermore, we use theoretical calculations of the partial wave composition of the absorption cross section just above the ionization threshold and the principle of continuity of oscillator strength through an ionization threshold to support this conclusion. The new absolute photoabsorption cross sections are discussed in light of these arguments, and the results are consistent with the expectations. This type of argument should be valuable for assessing the potential importance of different Rydberg series when sufficiently accurate direct quantum chemical calculations are difficult, for example, in the n ≥ 5 manifolds of excited states of larger moleculesShow less >

Language :

Anglais

Popular science :

Non

Collections :

• Institut d'Électronique, de Microélectronique et de Nanotechnologie (IEMN) - UMR 8520

Source :

Harvested from HAL