Pulse radiolysis of polystyrene in cyclohexane – Effect of carbon tetrachloride on kinetic dynamics of dimer radical cation−

Abstract The dependence of the kinetic dynamics of the polystyrene dimer radical cation ( Ph 2 + ) on the CCl4 concentration was investigated in a cyclohexane solution by nanosecond pulse radiolysis. A slow formation of ( Ph 2 + ) (k = 1.5 × 109 M−1 s−1) through electron transfer quenching of the polystyrene excimer was observed upon the addition of 10–100 mM CCl4. This electron transfer quenching led to an increase of the free ion yield (∼20%).

[1]  J. Baxendale,et al.  The study of fast processes and transient species by electron pulse radiolysis : proceedings of the NATO Advanced Study Institute held at Capri, Italy, 7-18 September, 1981 , 1982 .

[2]  C. Bojarski,et al.  Fluorescence quenching and singlet energy migration in polystyrene and its copolymers , 1986 .

[3]  M. Washio,et al.  Pulse radiolysis of polystyrene and benzene in cyclohexane, chloroform and carbon tetrachloride , 1983 .

[4]  A. O. Allen,et al.  IONIZATION OF LIQUIDS BY RADIATION STUDIED BY THE METHOD OF PULSE RADIOLYSIS. III. SOLUTIONS OF GALVINOXYL RADICAL. , 1970 .

[5]  K. Yoshihara,et al.  Formation of benzene dimer cations in neat liquid benzene studied by femtosecond transient absorption spectroscopy , 1997 .

[6]  S. Kashiwagi,et al.  Synchronization of femtosecond UV-IR laser with electron beam for pulse radiolysis studies , 2005 .

[7]  S. Tagawa,et al.  The formation process of the excited state of cycloalkane liquid using picosecond pulse radiolysis , 1982 .

[8]  S. Siegel,et al.  Nanosecond Pulse Radiolysis of Polystyrene and Poly(methylmethacrylate) , 1969 .

[9]  J. K. Thomas.  Observation of excited states in the radiolysis of liquid hydrocarbons , 1976 .

[10]  Photoinduced electron transfer dynamics in aromatic vinyl polymers and related systems: time-resolved detection of primary events , 2003 .

[11]  J. K. Thomas,et al.  Energy Transfer via Ionic Processes in Polymer Films Irradiated by 0.4 MeV Electrons , 1996 .

[12]  K. Yoshihara,et al.  Nanosecond laser photolysis of the benzene monomer and eximer , 1980 .

[13]  F. Bovey,et al.  Fluorescence of Styrene Homopolymers and Copolymers , 1963, Nature.

[14]  H. Miyasaka,et al.  Picosecond 266 nm laser photolysis studies on the excimer formation process of polystyrene in solution. Effects of temperature and degree of polymerization on the formation time constants , 1993 .

[15]  Masahide Yamamoto,et al.  Laser photolysis studies on the intramolecular dimer radical cations formed in 1,3-dipyrenylpropanes , 1991 .

[16]  W. Schnabel,et al.  Laser flash photolysis studies on excited singlet states of benzene, toluene, p-xylene, polystyrene, and poly-α-methylstyrene , 1980 .

[17]  H. Miyasaka,et al.  Femtosecond-picosecond laser photolysis studies on the dynamics of excited charge-transfer complexes in solution. 2. Ion pair formation processes in the excited states of 1,2,4,5-tetracyanobenzene-aromatic hydrocarbon complexes in polar solvents , 1990 .

[18]  Takahiro Kozawa,et al.  Study on intermediate species of polystyrene by using pulse radiolysis , 2001 .

[19]  M. Washio,et al.  Study on sensitized degradation and crosslinking of polymers by means of picosecond pulse radiolysis , 1985 .

[20]  W. Schnabel,et al.  On the mechanism of the photolysis of polystyrene in chloroform solution. Laser flash photolysis studies , 1980 .

[21]  Seiichi Tagawa,et al.  Intramolecular excimer formation of oligostyrenes from dimer to tridecamer: The measurements of rate constants for excimer formation, singlet energy migration, and relaxation of internal rotation , 1983 .

[22]  S. Tagawa,et al.  Picosecond pulse radiolysis studies on excitation processes in liquid cyclohexane , 1980 .

[23]  J. K. Thomas,et al.  Transport of Singlet Excitation in Solid Aromatic Polymers , 1995 .

[24]  P. Barbara,et al.  Ultrafast electron transfer in optically prepared simple' ion pairs. The mechanism at high donor concentration , 1995 .

[25]  Seiichi Tagawa,et al.  Electronic Structure of Radical Anions and Cations of Polysilanes with Structural Defects , 1999 .

[26]  J. K. Thomas,et al.  Spectroscopic Investigation of Photoinduced Charge Separation and Recombination in Solid Polymers , 1998 .

[27]  D. Rehm,et al.  Kinetics of Fluorescence Quenching by Electron and H‐Atom Transfer , 1970 .

[28]  A. O. Allen,et al.  Chemical reaction rates of quasifree electrons in nonpolar liquids. II , 1975 .