Comparison of chlorine dioxide photochemistry in acetonitrile and water using subpicosecond pump-probe spectroscopy

被引:37
作者
Philpott, MJ [1 ]
Charalambous, S [1 ]
Reid, PJ [1 ]
机构
[1] Univ Washington, Dept Chem, Seattle, WA 98195 USA
基金
美国国家科学基金会;
关键词
D O I
10.1016/S0009-2614(97)01164-0
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The photochemical reaction dynamics of chlorine dioxide (OClO) dissolved in water and acetonitrile are investigated using subpicosecond pump-probe spectroscopy. The spectral dynamics observed at 267 and 400 nm demonstrate that the quantum yield for geminate recombination of ClO and O to form OClO is reduced in acetonitrile relative to water. However, the dynamics at 800 nm are similar for both solvents consistent with ClOO rather than OClO being responsible for the evolution at this wavelength. The kinetics for ground-state ClOO production and decomposition are significantly slower in acetonitrile relative to water suggesting that solvent-solute hydrogen bonding is important in defining the ground state reactivity of this photoproduct. (C) 1997 Elsevier Science B.V.
引用
收藏
页码:1 / 9
页数:9
相关论文
共 33 条
[1]   ELECTRON-SPIN-RESONANCE INVESTIGATION OF THE PHOTOISOMERIZATION OF OCIO TO CIOO IN AN H2SO4 GLASS - MAGNETOPHOTOSELECTION AND KINETICS [J].
ADRIAN, FJ ;
BOHANDY, J ;
KIM, BF .
JOURNAL OF CHEMICAL PHYSICS, 1986, 85 (05) :2692-2698
[2]   MATRIX INFRARED STUDY OF C100 RADICAL [J].
ARKELL, A ;
SCHWAGER, I .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1967, 89 (24) :5999-&
[3]   GENERATION OF 11-FS PULSES FROM A SELF-MODE-LOCKED TI-SAPPHIRE LASER [J].
ASAKI, MT ;
HUANG, CP ;
GARVEY, D ;
ZHOU, JP ;
KAPTEYN, HC ;
MURNANE, MM .
OPTICS LETTERS, 1993, 18 (12) :977-979
[4]   MODE-SPECIFIC CHEMICAL BRANCHING RATIOS IN THE PHOTODISSOCIATION OF OCLO [J].
BISHENDEN, E ;
DONALDSON, DJ .
JOURNAL OF CHEMICAL PHYSICS, 1993, 99 (04) :3129-3132
[5]   PYRIDINE COMPLEXES OF CHLORINE ATOMS [J].
BRESLOW, R ;
BRANDL, M ;
HUNGER, J ;
TURRO, N ;
CASSIDY, K ;
KROGHJESPERSEN, K ;
WESTBROOK, JD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (23) :7204-7206
[6]   Ultrafast dynamics of chlorine dioxide photochemistry in water studied by femtosecond transient absorption spectroscopy [J].
Chang, YJ ;
Simon, JD .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (16) :6406-6411
[7]   CHARGE-TRANSFER ABSORPTION-SPECTRA OF CHLORINE ATOMS IN HALOGENATED SOLVENTS [J].
CHATEAUNEUF, JE .
CHEMICAL PHYSICS LETTERS, 1989, 164 (06) :577-580
[8]  
*CRC, 1993, CRC HDB CHEM PHYS
[9]   Photodissociation dynamics of OClO [J].
Davis, HF ;
Lee, YT .
JOURNAL OF CHEMICAL PHYSICS, 1996, 105 (18) :8142-8163
[10]   SOLVENT EFFECTS ON THE SPECTROSCOPY AND ULTRAFAST PHOTOCHEMISTRY OF CHLORINE DIOXIDE [J].
DUNN, RC ;
FLANDERS, BN ;
SIMON, JD .
JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (19) :7360-7370