Correlation between the atomic alignment and the alignment of XeX* (B, C) rotation in the reactions of oriented Xe ((3)P(2), M(J) = 2) + halogen (X)-containing molecules.
The polarization of the XeX* (B) and XeX* (C) emissions in the reactions of oriented Xe* ((3)P(2), M(J) = 2) + halogen (X)-containing molecules (CCl(4), CF(3)Br, CF(3)I, CH(3)I, NF(3)) has been measured as a function of each magnetic M(J)' substate in the collision frame. The parallel polarization of the XeX* (B, C) emissions to the relative velocity vector is commonly observed for all magnetic M(J)' substates. The correlation between the atomic alignment (M(J)') and the M(J)'-dependent alignment (A(M(J)')) of the XeX* (B, C) rotation is found to be extremely different between the XeX* (B) and XeX* (C) channels: For XeX* (B), A(M(J)') is highest for the M(J)' = 0 state, except CCl(4), whereas the |M(J)'| = 2 states give the highest A(M(J)') for XeX* (C). Alternatively, the correlation between the configuration (L(Z)') of the inner 5p orbital and the L(Z)'-dependent alignment (A(L(Z)')) of the XeX* (B, C) rotations is revealed. The collision with |L(Z)'| = 1 causes a similar positive alignment A(L(Z)') for the XeX* (B) and XeX* (C) channels. The alignment A(L(Z)') at the collision with |L(Z)'| = 0 is extremely different between the XeX* (B) and XeX* (C) channels. The collision with L(Z)' = 0 induces no alignment of XeX* (C) except CF(3)I, that is, A(L(Z)'=0) approximately 0, whereas it induces the higher positive A(L(Z)') of XeX* (B). The different M(J)' dependence on the alignment of the XeX* (B, C) rotation between the XeX* (B) and XeX* (C) channels can be recognized as the change of reaction mechanism due to the difference in the favorable impact parameter for each M(J)' state between the XeX* (B) and XeX* (C) channels, which reflects the Omega' conservation in the course of ion-pair (Xe(+)-RX(-)) formation.
Ohoyama
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Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
Yasuda
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Kasai
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