TY - JOUR AU - Vauthey, E. AU - Suppan, P. TI - Temperature Effect on Back Electron-Transfer Reactions within a Geminate Radical Pair: the Influence of the Solvent on the Adiabaticity of the Process PY - 1989 JF - Chemical Physics JA - Chem. Phys. SN - 0301-0104 VL - 139 IS - 2-3 SP - 381 EP - 390 L1 - http://www.sciencedirect.com/science?_ob=MImg&_imagekey=B6TFM-44GH8FS-P2-1&_cdi=5230&_orig=browse&_coverDate=12%2F15%2F1989&_sk=998609997&view=c&wchp=dGLbVzz-lSztb&_acct=C000043220&_version=1&_userid=779890&md5=3bc763c92c74253961911284a9bf65bd&ie=f.pdf L3 - http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6TFM-44GH8FS-P2&_user=779890&_handle=W-WA-A-A-WY-MsSAYWW-UUA-AUCUACCEAW-VEWEVAYYW-WY-U&_fmt=summary&_coverDate=12%2F15%2F1989&_rdoc=14&_orig=browse&_srch=%23toc%235230%231989%23998609997%23274450!&_cdi=5230&view=c&_acct=C000043220&_version=1&_urlVersion=0&_userid=779890&md5=037c6fc14fcad2a58f11e1bc62c5f4ba M3 - 10.1016/0301-0104(89)80150-8 UR - http://dx.doi.org/10.1016/0301-0104(89)80150-8 N2 - A study of the temperature dependence (from 233 to 353 K) of the rate of back electron-transfer reactions within geminate radical pairs by measurement of the free radical yield is reported. The radical pair is generated by photoinduced electron transfer with rhodamine 6G and oxazine 118 cations as electron acceptors and aromatic amines and methoxy-benzene derivatives as electron donors in acetonitrile, methanol and ethanol. In acetonitrile, the back electron transfer is non-adiabatic and apparent negative activation energies are observed for barrierless reactions. In alcohol solvents, an anomalously large temperature dependence is observed, which is attributed to a solvent-controlled adiabatic behaviour. ID - 127 ER -