RESUMEN
Time-resolved observations have been made of the formation of vibrationally excited NO X 2Π (v') following collisional quenching of NO A 2Σ+ (v = 0) by NO X 2Π (v = 0). Two time scales are observed, namely a fast production rate consistent with direct formation from the quenching of the electronically excited NO A state, together with a slow component, the magnitude and rate of formation of which depend upon NO pressure. A reservoir state formed by quenching of NO A 2Σ+ (v = 0) is invoked to explain the observations, and the available evidence points to this state being the first electronically excited state of NO, a 4Π. The rate constant for quenching of the a 4Π state to levels v' = 11-16 by NO is measured as (8.80 ± 1.1) × 10-11 cm3 molecule-1 s-1 at 298 K where the error quoted is two standard deviations, and from measurements of the increased formation of high vibrational levels of NO(X) by the slow process we estimate a lower limit for the fraction of self-quenching collisions of NO A 2Σ+ (v = 0) which lead to NO a 4Π as 19%.
RESUMEN
Collisional quenching of NO A2Σ+ (v = 0, 1) by O2 has been studied through the detection of vibrationally excited products by time-resolved Fourier transform infrared emission spectroscopy. Non-reactive quenching of NO A2Σ+ (v = 0) produces a vibrational distribution in NO X2Π which has been quantified for v = 2-22, and is found to be bimodal. The results are consistent with two quenching channels. The first forms the ground X3Σ or low-lying a 1Δg electronic state of O2 with a distribution including high vibrational levels of NO X2Π which is slightly hotter than statistical. Two possibilities are identified for the second channel. The first, with a similar quantum yield to that producing higher vibrational levels, forms a highly electronically excited state, such as O2 c1Σ, with low vibrational levels in NO X2Π which are inverted with a distribution resembling that resulting from a sudden or harpoon mechanism. The second is that ground state oxygen is formed with low vibrational energy partitioned into NO X2Π. In addition, vibrationally excited NO2 is observed, but at intensities which indicate that it is formed in low quantum yield. Quantitatively unobservable processes (defined as those which do not form ground state NO (v ≥ 2)) are found to have a branching ratio of at most 25 ± 5%. The results are compared with those of previous studies and the most consistent interpretation suggests that dissociation of O2 to form ground state O(3P) atoms and ground vibrational state NO X2Π (v = 0) is the main reactive process rather than NO2 formation. Qualitatively similar results are seen for the quenching of NO A2Σ+ (v = 1).
RESUMEN
Time-of-flight mass spectrometry reveals that atomic and small molecular triply charged cations exhibit extensive bond-forming chemistry, following gas-phase collisions with neutral molecules. These experiments show that at collision energies of a few eV, I(3+) reacts with a variety of small molecules to generate molecular monocations and molecular dications containing iodine. Xe(3+) and CS2(3+) react in a similar manner to I(3+), undergoing bond-forming reactions with neutrals. A simple model, involving relative product energetics and electrostatic interaction potentials, is used to account for the observed reactivity.
RESUMEN
Relative precursor-specific partial ionisation cross sections for the fragment ions formed following electron ionisation of sulfur dioxide (SO2) have been measured for the first time, from 30 to 200 eV, using time-of-flight mass spectrometry coupled with two-dimensional ion coincidence detection. These data quantify the yields of O(2+), O(+), SO(2+), S(+), O2(+), and SO(+) ions, relative to the formation of SO2(+), via single, double, and triple electron ionisation of SO2. Formation of O(2+), following electron-SO2 collisions, has been quantified for the first time. The data allow a first experimental estimate of the triple ionisation potential of SO2 (69.0 ± 3.6 eV), an energy in good agreement with a value derived in this study via computational chemistry. The triple ion combination S(+) + O(+) + O(+) is clearly detected following electron collisions with SO2 at electron energies markedly below the vertical energy for forming SO2(3 +). This observation is accounted for by the operation of a stepwise pathway to the formation of S(+) + 2O(+) which does not involve the formation of a molecular trication.