Valence electron spectra of the methyl halides and of methyl alcohol have been induced by means of the HeI resonance radiation at 21.22 eV. A large number of new vibrational bands are reported. The observation of these was facilitated by a high instrumental resolving power and fast data acquisition. In most cases the new bands are observed in 1
A
1→2
E transitions but also the electron band of the 1
A
1→2
A
1 transition of CH3I exhibits extensive progressions of closely spaced vibrational bands not previously reported. The vibrational structure of the 1
A
1→2
E transitions is affected by vibronic coupling. The structure of the 2e electron band of CH3Cl probably reflects the operation of the Ham effect. Calculations of the band structure including spin-orbit coupling are performed according to a model which is briefly described.
The complete valence shell photoelectron spectra of cytosine, thymine and adenine have been investigated experimentally and theoretically. Vertical ionization energies and spectral intensities have been evaluated using the many-body Green's function method, thereby enabling theoretical photoelectron spectra to be derived. In cytosine, the influence of tautomers and rotational conformers has been investigated. The calculated spectra display a satisfactory agreement with the experimental data and this has allowed most of the photoelectron bands to be assigned. Photoelectron asymmetry parameters have been determined from angle resolved spectra recorded with synchrotron radiation. The experimental data show that the electronic configuration of the five outer orbitals in cytosine, thymine and adenine is π, σ, π, σ, π. Vertical ionization energies have been measured for all the outer-valence orbitals even though some of the associated bands overlap significantly.
The absolute photoabsorption, photoionization and photodissociation cross sections and the photoionization quantum efficiency of ammonia and deuterated ammonia have been measured from the ionization threshold to 25 eV using a double ion chamber and monochromated synchrotron radiation. The photoabsorption spectrum displays extensive vibrational progressions associated with Rydberg series converging onto excited vibrational levels of the 2A2´´ state. New structure has been observed for ND3 in the 10.0-11.3 eV range, and vibrational progressions due to transitions into the , and Rydberg states have been recorded with improved resolution. Features have been observed, for the first time, in the photoabsorption spectra of NH3 and ND3 due to Rydberg series converging onto the à 2E ionization threshold, and interpretations for some of these features have been proposed based upon the corresponding photoelectron spectra.
The He I excited NH3+(1a2´´)-1 2A2´´ photoelectron band has been studied experimentally at a resolution of 3 meV and two vibrational progressions, each involving excitation of the 2+ mode, have been observed. The vibrational lines in the main progression show a complex structure associated with rotational excitations. This structure changes gradually in a way that can be explained by the variation of the H-N-H bond angle with the 2+ mode. The effective bond angle has been found to be 120° for v2+ = 0, and similar to that of the neutral ground state near v2+ = 6. The second progression, of weak lines, has been interpreted tentatively as being due to n2++4+. The 4+ mode is doubly degenerate and the excitation of a single quantum has been explained by vibronic coupling with the à 2E state. In addition, He II excitation has been used to record the entire valence shell photoelectron spectrum.
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