Perturbation-facilitated optical-optical double resonance spectroscopy of the h0[sub u][sup -]([sup 3]P[sub 1]) and H1[sub u]([sup 3]P[sub 1]) ion-pair states of I[sub 2]

Motohiro, Satoshi; Nakajima, Shinsuke; Ishiwata, Takashi
July 2002
Journal of Chemical Physics;7/1/2002, Vol. 117 Issue 1, p187
Academic Journal
Perturbation-facilitated optical-optical double resonance spectroscopy has been applied to study the h0[sup -, sub u] (³P[sub 1]) and H1[sub u](³P[sub 1]) ion-pair states of I[sub 2] correlating with I[sup -] ( ¹ S) + I[sup +] (³P[sub 1] ). The intermediate states used were the g/u parity mixed states found in the B ³Π(0[sup +, sub u])-X ¹&Sigma[sup +, sub g] absorption spectrum near the dissociation limit. We identified several B ³Π(0[sup +, sub u])∼³Π(0[sup -, sub g]) coupled states by hyperfine interactions for the first time. These states had the 0[sup +, sub u] and )[sub -, sub g] double-faced character and facilitated to combine the X ¹Σ[sup +, sub g] ground state with the h0[sup -, sub u](³P[sub 1]) state in the (1 + 1) photon excitation scheme following the optical selection rules for one-photon transition. We also accessed the H1[sub u](³P[sub 1]) state through the B ³Π(0[sup +, sub u])∼cl[sub g] mixed state, and elucidated the heterogeneous coupling between the h0[sup -, sub u](³P[sub 1]) and HI[sub u](³P[sub 1]) states. Our analyses covered the region of about 48 200 to 50 300 cm[sup -1], and gave the molecular parameters of the h0[sup -, sub u](³P[sub 1]) state valid for v=0-17 and those of the H1[sub u](³P[sub 1]) state for v=0-20. The ³Π(O[sup -, sub g]) state used as an intermediate state was analyzed through the dispersed h0[sup -, sub u](³P[sub 1])-³Π(0[sup -, sub g]) emission in conjunction with the Franck-Condon factor calculations, and the principle spectroscopic constants of the ³Π(0[sup -, sub g]) state were reported.


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