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Spectroscopy by Boschke F.L.

By Boschke F.L.

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1); these states are expected to be bent and to possess intravalency shell character. In each molecule the l A(u) ~- 1~or) transition excites a broad absorption band, which in N2 O ( ~ 180 nm) ~, 2os,2o6) is completely structureless. In CO2 ( ~ 148 nm) 6' 196,207) CS2 ( ~ 310 nm) 6' 208) and CSe2 ( ~ 385 nm) 2~176the absorption displays a complex vibrational band structure which is complicated by the effects of Renner-Teller interactions in the bent upper B2 and/or A2 states. In OCS ( ~ 225 nm) 6) and OCSe ( ~ 250 nm) 197' 199), diffuse vibrational progressions in the bending frequency v2' may be identified.

For example, the 2;~u) states which can be generated by intravalency shell or Rydberg excitation would be expected to form a conjugate pair 1) the lower of which would assume the greater contribution from the intravalency shell description (though still possessing a high degree of Rydberg character if it lies at high enough energy). Similarly, the t Ilcg) Rydberg state has the same symmetry as the intravalency shell state generated by the transition 27r(g) ~ 5 o(g), but since the latter transition is expected to lie at energies above, or close to, the ~X~u) state, it also assumes a high degree of Rydberg character and is generally identified as the first member of the 27r(g) ~ nsotg ) Rydberg Series6' 196-198).

2 cm -1 130) 51 M. N. R. Ashfold, M. T. Macpherson,and J. P. Simons region of intense absorption assigned to population of the l X+ state in OCS (see Fig. 1). As in CO2, the correlation diagram (Fig. +) + S(1S). 3) but experiments to date suggest this route to be of minor importance only. , > 110 rim, but < 10% of the photodissociation yield could be attributed to primary production of CS. The relative contributions of SC-O and S-CO cleavage have also been estimated by using resonance fluorescence techniques to measure the initial concentrations of O(3p) and S(3P) following flash photolysis of OCS in an atmosphere of Ar at ;k > 105 nI~ 247).

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