Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 1497 - 1502 (1981)
Update date:2022-08-29
Topics:
Fox, Malcolm F.
Smith, Clifford B.
Hayon, Elie
The far-ultraviolet solution of very dilute thiocyanate ion in a range of solvents shows that there are at least three absorption bands labelled A, D and E.All three bands are shown to have charge-transfer-to-solvent charasteristics, in contrast to some previous reports.The conflicting previous reports of the spectroscoy and photochemistry of thiocyanate ions, together with the current work, are resolved in terms of a spectroscopic transition scheme involving a forbidden at ca. 36 000 cm-1, which is normally extremely weak or not detectable.The transition is only detected at high contrentrations of salt.The first allowed transition is expected to occur at ca. 62 000 cm-1.Within this scheme the c.t.t.s. bands occur (in aqueous solution) at 46 000 and 53 500 cm-1.A further band is observed in red-shifting solvents at ca. 57 000 cm -1.The temperature sensitivities of the three c.t.t.s. bands, relative to the solvated electron, are 0.58, 0.47 and 0.30.
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