Identification of the ns and nd Rydberg states of O2 for n=3–5

The 4s‐3d and 5s‐4dRydberg complexes of diatomic oxygen have been studied by (2+1) resonance‐enhanced multiphoton ionization of the X  3∑ g − ground state of O2. We have located and identified at least two vibrational levels of each of the following states: Three of four expected 4sσ Π states; all four expected 5sσ Π states; 18 of 22 expected 3d states (with only the states of the 3dσ orbital remaining unobserved); and 5 of the 10 predicted 4dπ states. State assignments were assisted by the following: the results of rotational cooling and laser polarization experiments which facilitated the rotational analysis, band positions, band intensities, and parameterized calculations. The experimentally determined state locations are compared with the state locations obtained from ab initio calculations. We have carried out isotope experiments and rotational linewidth analysis to study in some detail the mixing between the Rydberg states and the repulsive valence states as well as the mixing between the Rydberg states themselves. We conclude that direct predissociation dominates indirect predissociation as a dissociative mechanism, but there is evidence of Δv≠0 interactions which perturb the rotational structure of the 3dπ∑ and Δ states. The relative intensities of the states detected are found to span a range in excess of 104 with the nsσ Π states being the weakest and the ndπ ∑ states being the strongest. Photoionization of the ndπ ∑ states appears to be most affected by the shape resonance in the continuum. Our measurements confirm the expectation that many of the properties of the Rydberg states in the same series scale as (n*)−3

Identification of the nd Δ and Σ States and the 1,3Φ←←X 3Σ− g Transition of O2 by Resonant Multiphoton Ionization

Spectra of the 3dRydberg state region of O2 have been obtained by two‐photon resonant ionization of the ground electronic state. By varying the rotational distribution and radiation polarization, all observed bands were identified and attributed to excitation of Σ, Δ, and Φ states. Earlier assignments were corrected. The Δ and Φ assignments are complete while the Σ assignments are so far incomplete

A Halomethane thermochemical network from iPEPICO experiments and quantum chemical calculations

Internal energy selected halomethane cations CH3Cl+, CH2Cl2+, CHCl3+, CH3F+, CH2F2+, CHClF2+ and CBrClF2+ were prepared by vacuum ultraviolet photoionization, and their lowest energy dissociation channel studied using imaging photoelectron photoion coincidence spectroscopy (iPEPICO). This channel involves hydrogen atom loss for CH3F+, CH2F2+ and CH3Cl+, chlorine atom loss for CH2Cl2+, CHCl3+ and CHClF2+, and bromine atom loss for CBrClF2+. Accurate 0 K appearance energies, in conjunction with ab initio isodesmic and halogen exchange reaction energies, establish a thermochemical network, which is optimized to update and confirm the enthalpies of formation of the sample molecules and their dissociative photoionization products. The ground electronic states of CHCl3+, CHClF2+ and CBrClF2+ do not confirm to the deep well assumption, and the experimental breakdown curve deviates from the deep well model at low energies. Breakdown curve analysis of such shallow well systems supplies a satisfactorily succinct route to the adiabatic ionization energy of the parent molecule, particularly if the threshold photoelectron spectrum is not resolved and a purely computational route is unfeasible. The ionization energies have been found to be 11.47 ± 0.01 eV, 12.30 ± 0.02 eV and 11.23 ± 0.03 eV for CHCl3, CHClF2 and CBrClF2, respectively. The updated 0 K enthalpies of formation, ∆fHo0K(g) for the ions CH2F+, CHF2+, CHCl2+, CCl3+, CCl2F+ and CClF2+ have been derived to be 844.4 ± 2.1, 601.6 ± 2.7, 890.3 ± 2.2, 849.8 ± 3.2, 701.2 ± 3.3 and 552.2 ± 3.4 kJ mol–1, respectively. The ∆fHo0K(g) values for the neutrals CCl4, CBrClF2, CClF3, CCl2F2 and CCl3F and have been determined to be –94.0 ± 3.2, –446.6 ± 2.7, –702.1 ± 3.5, –487.8 ± 3.4 and –285.2 ± 3.2 kJ mol–1, respectively

PHOTOIONIZATION OF CH3NO2CH_{3}NO_{2}, C2H3ONO2C_{2}H_{3}ONO_{2}, AND C2H5NO2C_{2}H_{5}NO_{2}, ELECTRON AFFINITIES OF NO2NO_{2} AND NO3NO_{3}, AND THE HEAT OF FORMATION OF NO2NO_{2}

Author Institution: Department of Chemistry, Michigan State University; Department of Chemistry, Argonne National LaboratoryThe photoionization mass spectra of methyl and ethyl nitrate were investigated. Using the appearance potential of $C_{2}H$$^{+}_{5}$ from $C_{2}H_{5}ONO_{2}$, combined with well established thermodynamic data, the heat of formation of $NO_{3}$ was found to be 10.8 $\pm$ 1.0 kcal/mole. Various negative ions can be formed by the transfer of “nearly-zero-energy” electrons from electronically excited argon atoms to a series of parent nitro and nitrate molecules. Consideration of the relative energetics of these reactions leads to limiting values for the electron affinities: E.A. (NO) $\geq$ 2.90 eV; 2.15 $\leq$ E.A. ($NO_{2}\pm\leq 2.4$ eV