Picosecond kinetic study of the photoinduced homolysis of benzhydryl acetates: The nature of the conversion of radical pairs into ion pairs

被引：8

作者：

Heeb, Libby R. ^{[1
]}

Peters, Kevin S. ^{[1
]}

机构：

[1] Univ Colorado, Dept Chem & Biochem, Boulder, CO 80309 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2008年 / 130卷 / 05期

关键词：

D O I：

10.1021/ja077105n

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The conversion of benzhydryl acetate geminate radical pairs to contact ion pairs following photoinduced homolysis in solution is studied using picosecond pump-probe spectroscopy. The dynamics for the decay of the geminate radical pairs into contact ion pairs is modeled within a Marcus-like theory for nonadiabatic electron transfer. A second decay channel for the geminate radical pairs is diffusional separation to free radicals. The kinetics of this latter process reveals an energy of interaction between the two radicals in the geminate pair.

引用

页码：1711 / 1717

页数：7

共 40 条

[1] Experimental verification of the Smoluchowski theory for a bimolecular diffusion-controlled reaction in liquid phase [J].

Arita, T ;

Kajimoto, O ;

Terazima, M ;

Kimura, Y .

JOURNAL OF CHEMICAL PHYSICS, 2004, 120 (15) :7071-7074

[2] PHOTO-HETEROLYSIS AND PHOTO-HOMOLYSIS OF SUBSTITUTED DIPHENYLMETHYL HALIDES, ACETATES, AND PHENYL ETHERS IN ACETONITRILE - CHARACTERIZATION OF DIPHENYLMETHYL CATIONS AND RADICALS GENERATED BY 248-NM LASER FLASH-PHOTOLYSIS [J].

BARTL, J ;

STEENKEN, S ;

MAYR, H ;

MCCLELLAND, RA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (19) :6918-6928

[3] Mechanism of substitution at a saturated carbon atom Part XXV Unimolecular halogen exchange between an alkyl halide and halide ions in sulphur dioxide solution, and a concluding note [J].

Bateman, LC ;

Hughes, ED ;

Ingold, CK .

JOURNAL OF THE CHEMICAL SOCIETY, 1940, :1017-1029

[4] CONTROL OF PRODUCT DISTRIBUTION BY MARCUS TYPE ELECTRON-TRANSFER RATES FOR THE RADICAL PAIR GENERATED IN BENZYLIC ESTER PHOTOCHEMISTRY [J].

DECOSTA, DP ;

PINCOCK, JA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (24) :8948-8950

[5] Picosecond kinetic study of the photoinduced homolysis and heterolysis of diphenylmethyl bromide .1. The nature of the conversion from radical pairs to ion pairs [J].

Dreyer, J ;

Peters, KS .

JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (37) :15156-15161

[6] Picosecond kinetic study of the photoinduced homolysis and heterolysis of diphenylmethyl bromide .2. Role of polarization caging in contact ion pair recombination [J].

Dreyer, J ;

Lipson, M ;

Peters, KS .

JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (37) :15162-15164

[7]

FISCHER SF, 1977, CHEM PHYS, V26, P9, DOI 10.1016/0301-0104(77)87086-9

[8]

Gardiner Jr W.C., 1969, RATES MECH CHEM REAC

[9] RADIATIVE AND NONRADIATIVE ELECTRON-TRANSFER IN CONTACT RADICAL-ION PAIRS [J].

GOULD, IR ;

NOUKAKIS, D ;

GOMEZJAHN, L ;

YOUNG, RH ;

GOODMAN, JL ;

FARID, S .

CHEMICAL PHYSICS, 1993, 176 (2-3) :439-456

[10]

HEHRE WJ, 1998, BRIEF GUIDE MOL MECH

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