Electronic states of organic molecules. 3. Photoelectron spectra of cycloalkenes and methylenecycloalkanes

1976 ◽  
Vol 98 (23) ◽  
pp. 7179-7182 ◽  
Author(s):  
Kenneth B. Wiberg ◽  
G. Barney Ellison ◽  
John J. Wendoloski ◽  
C. R. Brundle ◽  
N. A. Kuebler
Keyword(s):  
Organic Molecules ◽  
Electronic States ◽  
Photoelectron Spectra

ChemInform Abstract: ELECTRONIC STATES OF ORGANIC MOLECULES. 3. PHOTOELECTRON SPECTRA OF CYCLOALKENES AND METHYLENECYCLOALKANES

1977 ◽  
Vol 8 (6) ◽  
pp. no-no
Author(s):  
K. B. WIBERG ◽  
G. B. ELLISON ◽  
J. J. WENDOLOSKI ◽  
C. R. BRUNDLE ◽  
N. A. KUEBLER
Keyword(s):  
Organic Molecules ◽  
Electronic States ◽  
Photoelectron Spectra

VUV FRAGMENTATION OF SOME HYDROFLUOROCARBON CATIONS STUDIED USING COINCIDENCE TECHNIQUES

2002 ◽  
Vol 09 (01) ◽  
pp. 153-158 ◽  
Author(s):  
WEIDONG ZHOU ◽  
D. P. SECCOMBE ◽  
R. Y. L. CHIM ◽  
R. P. TUCKETT
Keyword(s):  
Kinetic Energy ◽  
Ab Initio ◽  
Ground State ◽  
Lower Energy ◽  
Lone Pair ◽  
Electronic States ◽  
Photoelectron Spectra ◽  
Highest Occupied Molecular Orbital ◽  
Impulsive Model ◽  
Lone Pair Electrons

Threshold photoelectron–photoion coincidence (TPEPICO) spectroscopy has been used to investigate the decay dynamics of the valence electronic states of the parent cation of several hydrofluorocarbons (HFC), based on fluorine-substituted ethane, in the energy range 11–25 eV. We present data for CF 3– CHF 2, CF 3– CH 2 F , CF 3– CH 3 and CHF 2– CH 3. The threshold photoelectron spectra (TPES) of these molecules show a common feature of a broad, relatively weak ground state, associated with electron removal from the highest-occupied molecular orbital (HOMO) having mainly C–C σ-bonding character. Adiabatic and vertical ionisation energies for the HOMO of the four HFCs are presented, together with corresponding values from ab initio calculations. For those lower-energy molecular orbitals associated with non-bonding fluorine 2pπ lone pair electrons, these electronic states of the HFC cation decay impulsively by C–F bond fission with considerable release of translational kinetic energy. Appearance energies are presented for formation of the daughter cation formed by such a process (e.g. CF 3– CHF +), together with ab initio energies of the corresponding dissociation channel (e.g. CF 3– CHF + + F ). Values for the translational kinetic energy released are compared with the predictions of a pure-impulsive model.

Electronic states of organic molecules. I. Potential functions for the deformation of methane

1976 ◽  
Vol 98 (5) ◽  
pp. 1212-1218 ◽  
Author(s):  
Kenneth B. Wiberg ◽  
G. Barney Ellison ◽  
John J. Wendoloski
Keyword(s):  
Organic Molecules ◽  
Electronic States ◽  
Potential Functions

scholarly journals Interference stabilization of autoionizing states in molecular N2 studied by time- and angular-resolved photoelectron spectroscopy

2016 ◽  
Vol 194 ◽  
pp. 509-524 ◽  
Author(s):  
Martin Eckstein ◽  
Nicola Mayer ◽  
Chung-Hsin Yang ◽  
Giuseppe Sansone ◽  
Marc J. J. Vrakking ◽  
...  
Keyword(s):  
Decay Rate ◽  
Photoelectron Spectroscopy ◽  
Rydberg States ◽  
Electronic States ◽  
The Other ◽  
Photoelectron Spectra ◽  
Angular Distributions ◽  
Velocity Map Imaging ◽  
Imaging Spectrometer ◽  
Exponential Decay Rate

An autoionizing resonance in molecular N2 is excited by an ultrashort XUV pulse and probed by a subsequent weak IR pulse, which ionizes the contributing Rydberg states. Time- and angular-resolved photoelectron spectra recorded with a velocity map imaging spectrometer reveal two electronic contributions with different angular distributions. One of them has an exponential decay rate of 20 ± 5 fs, while the other one is shorter than 10 fs. This observation is interpreted as a manifestation of interference stabilization involving the two overlapping discrete Rydberg states. A formalism of interference stabilization for molecular ionization is developed and applied to describe the autoionizing resonance. The results of calculations suggest, that the effect of the interference stabilization is facilitated by rotationally-induced couplings of electronic states with different symmetry.

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