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Extra resources for The Thiol Group - Volume 1
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1. Gcneral and theoretical aspects 39 Therefore, neither CH,-S- nor the linear (L) structure CH,-S-H has a barrier to rotation, while CH,-SH ( S or E) has one, and CH,-CH,-SH, two barriers to rotation (a double rotor): If the two independent rotational modes of motion are labelled as 6$ and 8 2 then a n energy surface E(B,, B2) is generated, having cross-sections E(8,) and E(82) which will exhibit the characteristic barrier height. A segment of such a surface is illustrated schematically in Figure 23.
4475 Taken from Table 1 1 . * Taken from references 2, 3, 6 and 14. 67 kcnl/mole. V. excitation, vertical and non-vertical transitions for both ionization and electron capture should be distinguished. Tlie vertical ionization potential (IP,,) is always higher than the adiabatic ionization potential (IPJ while a vertical electron capture involves a smaller electron aflinity than that of tlic adiabatic process. This is because the anion has a slightly shorter bond length than the neutral species while the bond length of the cation is considerably 1on ger.
G. Csizniadia 34 concluded that RSI-I compounds are more acidic and more basic in the gas phase than the corresponding oxygen analogues". It should be pointed o u t that protonation almost always (even in the case of CH,) lowers the energy of the system, that is, the calculated proton affinity is negative. ) For this reason one cannot correlate gas phase acidity (or basicity) with solution acidity (or basicity) because solvation may markedly alter the situation with respect to the gas phase. However, gas phase acidity and basicity measurements are suitable for correlation with molecular structure since solvation does not mask the energy change in the course of proton capture or ejection.