Photoionization efficiency, compared with

Photoionization at 193 nm in oxygenated solution of poly(C) causes strand breakage with high efficiency, half of which occurs at times < 4 ms, the other half with a half-life of 7 ms (Melvin et al. 1996 Table 11.8). This kinetic behavior is very different from what is seen after -OH-attack and points to the direct involvement of the Cyt radical cation. In poly(U), the (biphotonic) photoionization shows similar results (Table 11.8). With poly(A), the formation of strand breaks is 20-times less efficient as compared to poly(C) (Table 11.8), and this is in agreement with the above conclusion that the A-+ or A- do not cause strand breakage to any major extent. 

Ranha et al. [5] compared the ionization efficiency for flavonoids with ESI, APCl, and atmospheric-pressure photoionization (APPI) with nine different mobile-phase compositions in both positive-ion and negative-ion mode. The mobile-phase composition can have distinct influence on the response. Best response was achieved with 0.4% formic acid (pH 2.3) for positive-ion ESI and APCl, with 10 mmol/1 ammonium acetate adjusted to pH 4.0 for negative-ion ESI and APCl, and with 5 mmol/1 ammonium acetate in APPI. 

These results indicate that long lived autoionization states with excitation cross-sections comparable to those for excitation of bound high-lying states exist in heavy atoms with complex spectra. Transitions to these autoionization states can radically increase the efficiency of photoionization of atoms, a factor very important in atomic vapor laser isotope separation. 

Photoionization of the hydrocarbon followed by dissociative electron attachment (Reaction 1) should be considered since the ionization potential of a molecule is less in the liquid phase than it is in the gas phase. For hydrocarbons the ionization potential is 1 to 1.5 e.v. less in the liquid phase (24). The photon energy at 1470 A. is about 1.4 e.v. below the gas-phase ionization potentials of cyclohexane and 2,2,4-trimethylpentane (14). Some ionization may therefore occur, but the efficiency of this process is expected to be low. Photoionization is eliminated as a source of N2 for the following reasons. (1) If photoionization occurred and the electron reacted with nitrous oxide, then O" would be formed. It has been shown in the radiolysis of cyclohexane-nitrous oxide solutions that subsequent reactions of O result in the formation of cyclohexene and dicyclohexyl (I, 16, 17) and very little cyclohexanol (16, Table III). In the photolysis nitrous oxide reduces the yield of cyclohexene and does not affect the yield of dicyclohexyl. This indicates that O is not formed in the photolysis, and consequently N2 does not result from electron capture. (2) A further argument against photoionization is that cyclohexane and 2,2,4-trimethylpentane have comparable gas-phase ionization potentials but exhibit quite different behavior with respect to N2 formation. 

From Eq. (9) it is clear that correct determination of QY depends on accurate knowledge of the overall detection efficiency/, which is generally about 0.5. It can be determined in two ways. One is to compare the measured ratio C2+/C+ with the calculated ratio for an atomic rare gas such as Xe at a wavelength where the true relative production ratio A2+/N+ is known from photoionization mass spectrometric measurement of the ion yields. This method has been used in deriving the Xe data of Fig. 15. As expected, the quantum yield in the atomic case is unity (100%) within experimental error this must be generally true because deactivation of superexcited states by light emission is very rare. Thus the second and quicker method is simply to measure the apparent QY for an atomic gas and determine / accordingly. 

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