Energy dependence of the differential photoelectron cross sections of molecular nitrogen

The angular distribution of photoelectron intensity for molecular nitrogen was studied using He I and Ne I resonance line discharge light sources. Studies of photoelectron angular distributions covering a range of photon energies, and thus a range of photoelectron energies, are possible using the weaker high order lines in each discharge as well as the principal lines. Peaks in three photoelectron bands of N_2 were studied at the photon energies 16.85, 19.78, 21.22, 23.09, and 23.74 eV, where possible. We find that the v′=0 peak of the X^ 2Σ^+_g band has abnormally high intensity and, at the higher photon energies, an abnormally low angular distribution asymmetry parameter, β. Several mechanisms for this anomaly are discussed, including autoionization, the variation of electric dipole transition moments with internuclear distance, and possible shape resonance phenomena. None of these explanations is completely in agreement with all theoretical and experimental evidence

Energy Threshold for D+H_2→DH+H Reaction

We have been able to measure the threshold energy Eo for the reaction D+H_2→DH+H. The value obtained was (0.33±0.02) eV. Apparently, this is the first direct determination of a threshold energy for a reaction involving the formation and breaking of covalent bond

Photoelectron spectroscopy of ethylene, isobutylene, trimethylethylene, and tetramethylethylene at variable angles

Using a HeI line 58.4 nm source lamp, photoelectron angular distributions were measured for the series of four olefins: ethylene, isobutylene (2‐methyl‐propene), trimethylethylene (2‐methyl‐2‐butene), and tetramethylethylene (2,3‐dimethyl‐2‐butene). From these, the asymmetry parameter β as a function of photoelectron energy was obtained for each of these molecules. The following important effects in the behavior of β are observed: (a) In the π orbital ionization regions of the spectrum of each molecule, β increases with increasing electron energy across the vibrational envelopes. (b) With increasing methyl substitution (and at a fixed photoelectron enegy) β for this band decreases. (c) In the region of the spectra of each of the methyl‐substituted ethylenes involving several 2pσ bands, this energy dependence of β behaves as if they constituted a single band, in spite of the widely differing orbital symmetries. (d) Over most of the 2pσ region of each molecule, β decreases with increasing photoelectron energy, except for the high ionization potential end of this region, where β increases instead. We attribute effects (b) and (d) to σ–π orbital mixing

Determination of Electronic Energy Levels of Molecules by Low-Energy Electron Impact Spectroscopy

This paper describes a new spectroscopic tool in which optically forbidden electronic transitions can usually be detected as clearly as optically allowed ones in a fairly routine manner. It uses the inelastic scattering of low-energy electrons by molecules as the means for determining their electronic energy levels

Differences between Low-Energy Electron Impact Spectra at 0º and at Large Scattering Angle

The preceding Comment reports some low-energy electron-impact spectra of helium and ethylene, obtained by a very elegant technique, which are markedly different from the ones we obtained 1 under other experimental conditions. It is quite important to try to understand the reasons for the differences observed. These differences are essentially the following: (a) In our impact spectra of helium obtained with 50-eV electrons we observe pronounced peaks corresponding to the 2 ^3S state and to ionization whereas Simpson and Mielczarek do not. (b) In our spectra of ethylene at this same incident electron energy we observe two pronounced optically forbidden transitions an

Variable angle photoelectron spectrometer

The design, construction, and performance of a spectrometer for measuring the angular and energy distributions of electrons photoejected by rare gas resonance light is described. Results using 584.4‐Å photons from a helium lamp are reported. Flexibility of instrumental design allows for the use of other light sources. A 180° hemispherical electrostatic electron energy analyzer is rotatable about the center of an enclosed sample chamber. The instrument is highly automated, with an on‐line computer used to control the detector angle and the data acquisition and reduction. This automation is required by the long and continuous data acquisition

Exact quantum quasiclassical, and semiclassical reaction probabilities for the collinear F+D_2 → FD+D reaction

Exact quantum, quasiclassical, and semiclassical reaction probabilities and rate constants for the collinear reaction F+D_2 → FD+D are presented. In all calculations, a high degree of population inversion is predicted with P^R_(03) and P^R(04) being the dominant reaction probabilities. In analogy with the F+H_2 reaction (preceding paper), the exact quantum 0→3 and 0→4 probabilities show markedly different energy dependence with PR03 having a much smaller effective threshold energy (E_T=0.014 eV) than P^R_(04) (0.055 eV). The corresponding quasiclassical forward probabilities P^R_(03) and P^R_(04) are in poor agreement with the exact quantum ones, while their quasiclassical reverse and semiclassical counterparts provide much better approximations to the exact results. Similar comparisons are also made in the analysis of the corresponding EQ, QCF, QCR, and USC rate constants. An information theoretic analysis of the EQ and QCF reaction probabilities indicates nonlinear surprisal behavior as well as a significant isotope dependence. Additional quantum results at higher energies are presented and discussed in terms of threshold behavior and resonances. Exact quantum reaction probabilities for the related F+HD → FH+D and F+DH → FD+H reactions are given and an attempt to explain the observed isotope effects is made

Large quantum effects in the collinear F+H2-->FH+H reaction

We have performed accurate quantum mechanical calculations of reaction probabilities for the collinear F+H2-->FH+H reaction as well as corresponding quasiclassical trajectory calculations. A comparison of these results shows that very significant quantum mechanical effects are present in this reaction

Electron-Impact Spectroscopy

A spectrometer has been devised for determining electronic energy levels of molecules by inelastic scattering of low-energy electrons. It permits the detection of optically forbidden electronic transitions as clearly as optically allowed ones in a routine manner. The spectrometer has been used to obtain excitation spectra for helium, argon, hydrogen and ethylene. For the first three of these substances, the spectra agree with previous experiments. For ethylene, in addition to optically allowed transitions, two forbidden ones occur at about 4-6 and 6-5eV. Variation of peak heights with incident electron beam energy suggest that the first corresponds to a triplet state but that the second does not