Photoelectron spectra and orbital interactions in methylenenortriquinacenes

1978 ◽  
Vol 100 (1) ◽  
pp. 100-105 ◽  
Author(s):  
L. N. Domelsmith ◽  
K. N. Houk ◽  
C. R. Degenhardt ◽  
L. A. Paquette
Keyword(s):  
Photoelectron Spectra ◽  
Orbital Interactions

ChemInform Abstract: PHOTOELECTRON SPECTRA AND ORBITAL INTERACTIONS IN METHYLENENORTRIQUINACENES

1978 ◽  
Vol 9 (17) ◽  
Author(s):  
L. N. DOMELSMITH ◽  
K. N. HOUK ◽  
C. R. DEGENHARDT ◽  
L. A. PAQUETTE
Keyword(s):  
Photoelectron Spectra ◽  
Orbital Interactions

A Photoelectron Investigation of the Peroxide Bond

1975 ◽  
Vol 53 (22) ◽  
pp. 3439-3447 ◽  
Author(s):  
R. S. Brown
Keyword(s):  
Dihedral Angle ◽  
Ground State ◽  
Vibrational Frequencies ◽  
Molecular Orbitals ◽  
Photoelectron Spectra ◽  
Raman Spectroscopic ◽  
Orbital Interactions ◽  
Highest Occupied Molecular Orbitals ◽  
Peroxide Bond

The photoelectron spectra of several peroxides and their interpretation is presented. The effects of substituents is separated from vicinal orbital interactions using as a guideline the effect of similar substitution on the ether analogues. It is found that by comparison of Raman spectroscopic frequencies of the peroxide ground state, and vibrational frequencies for the ion (via pes), that the HOMO of peroxides is antibonding with respect to the O—O linkage. Additionally, the dependence of the splitting of the two highest occupied molecular orbitals on dihedral angle is verified by the pe spectra of several well-defined cyclic peroxides. Finally, the pe spectrum of tetramethyl-1,2-dioxacyclobutane (tetramethyl dioxetane) is presented indicating that it is not unlike other cyclic peroxides.

Application of photoelectron spectroscopy to intramolecularly hydrogen-bonded systems. Part IV. π-Systems; the photoelectron spectra of syn- and anti-7-norbornenol

1976 ◽  
Vol 54 (20) ◽  
pp. 3206-3209 ◽  
Author(s):  
R. S. Brown
Keyword(s):  
Hydrogen Bond ◽  
Photoelectron Spectroscopy ◽  
Ionization Energy ◽  
Geometric Isomer ◽  
Photoelectron Spectra ◽  
Orbital Interactions ◽  
The Difference ◽  
Hydrogen Bonded Systems ◽  
Intramolecular Hydrogen ◽  
Hydrogen Bonded

In an effort to determine the effect of an intramolecular hydrogen bond on the ionization energy of a simple π-system, the photoelectron spectra of syn- and anti-7-norbornenol have been determined. The difference in the ionization energy of the π(C—C) and nÖH orbitals is 0.30 eV for the former, and 0.85 eV for the latter. The photoelectron spectrum of the syn- isomer shows that the π(C—C) bond is roughly 0.2 eV more difficult to ionize than its counter-part in the non-hydrogen bonded geometric isomer and has been interpreted as arising from hydrogen bond induced stabilization of the π-bond. That the spectral differences in the alcohols is not simply due to differing orbital interactions between the two isomers can be demonstrated by the photoelectron spectra of syn- and anti-7-methoxynorbornene. In these systems which allow no possibility of hydrogen bonding the π(C—C) – nÖR difference is the same for both isomers.

Orbital interactions. XI. Application of photoelectron spectroscopy to the study of orbital interactions in some 2- and 9-substituted octahydrodimethanonaphthalenes

1982 ◽  
Vol 35 (2) ◽  
pp. 293 ◽  
Author(s):  
MN Paddon-Row ◽  
HK Patney ◽  
RS Brown
Keyword(s):  
Photoelectron Spectroscopy ◽  
Photoelectron Spectra ◽  
Anti Isomer ◽  
Orbital Interactions

The photoelectron spectra of some 2- and 9-substituted (1x,4x,4aβ,5β,8β,8aβ)-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalenes, (1)-(6), and (12), and their perhydro analogues, (1')-(6'), and (12'), were obtained in order to assess the magnitude and nature of orbital interactions in these molecules. The πcc Ip of the ketone (12) was found to be 0.1 eV higher than that of the hydrocarbon (1) and is thought to be due to the presence of orbital interactions through bonds in the former molecule. Through-space and through-bond interactions in the ketone (6) are responsible for increasing the πcc Ip by 0.33 eV with respect to that of (1) whereas through-space interactions are solely responsible for the lowering of the πcc Ip of the syn-ether (5) 0.36 eV with respect to the anti isomer (3). Strong intramolecular OH…π bonding in the alcohol (4) results is an increase in πcc by 0.33 eV and a decrease in the no Ip by 0.42 eV both with respect to the corresponding ionizations in the anti-alcohol (2).

Orbital interactions in α-carbofunctional silanes

1975 ◽  
Vol 40 (8) ◽  
pp. 2309-2314 ◽  
Author(s):  
R. Ponec ◽  
V. Chvalovský
Keyword(s):  
Orbital Interactions
Sign in / Sign up

Export Citation Format

Share Document