Ultrafast dynamics of chlorine dioxide photochemistry in water studied by femtosecond transient absorption spectroscopy

被引:46
作者
Chang, YJ
Simon, JD
机构
[1] UNIV CALIF SAN DIEGO,DEPT CHEM & BIOCHEM,LA JOLLA,CA 92093
[2] UNIV CALIF SAN DIEGO,INST NONLINEAR SCI,LA JOLLA,CA 92093
关键词
D O I
10.1021/jp953285o
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 ultrafast dynamics of chlorine dioxide (OClO) photochemistry in aqueous solution was studied by femtosecond transient absorption spectroscopy. Following the photoexcitation of OClO at 395 nm, the transient absorption dynamics were probed at 12 different wavelengths ranging from 350 to 700 nm, The transient absorption features observed in the visible wavelengths are assigned to correspond to the vibrationally hot photoisomer ClOO*. The spectral dynamics reveal the vibrational relaxation of this molecule in its ground electronic state. The total vibrational energy relaxation occurs within similar to 9 ps. The dynamics of the formation of chlorine atom was examined by measuring the absorption dynamics in the 350-390 nm range. The time constant for Cl formation is calculated to be similar to 200 ps. The data show that the dominant pathway for Cl formation is via the isomerized ClOO molecule. No fast component for Cl is detected, indicating that the ClOO molecule reaches thermal equilibrium before dissociating into Cl and O-2.
引用
收藏
页码:6406 / 6411
页数:6
相关论文
共 46 条
[31]   ON THE RELEVANCE OF OCLO PHOTODISSOCIATION TO THE DESTRUCTION OF STRATOSPHERIC OZONE [J].
LAWRENCE, WG ;
CLEMITSHAW, KC ;
APKARIAN, VA .
JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 1990, 95 (D11) :18591-18595
[32]   VIBRATIONAL AND ROTATIONAL RELAXATION-TIMES OF SOLVATED MOLECULAR-IONS [J].
LI, M ;
OWRUTSKY, J ;
SARISKY, M ;
CULVER, JP ;
YODH, A ;
HOCHSTRASSER, RM .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5499-5507
[33]   ULTRAFAST INVESTIGATION OF CONDENSED PHASE CHEMICAL-REACTION DYNAMICS USING TRANSIENT VIBRATIONAL SPECTROSCOPY - GEMINATE RECOMBINATION, VIBRATIONAL-ENERGY RELAXATION, AND ELECTRONIC DECAY OF THE IODINE A' EXCITED-STATE [J].
LINGLE, R ;
XU, XB ;
YU, SC ;
ZHU, HP ;
HOPKINS, JB .
JOURNAL OF CHEMICAL PHYSICS, 1990, 93 (08) :5667-5680
[34]   SLOW VIBRATIONAL-RELAXATION IN PICOSECOND IODINE RECOMBINATION IN LIQUIDS [J].
NESBITT, DJ ;
HYNES, JT .
JOURNAL OF CHEMICAL PHYSICS, 1982, 77 (04) :2130-2143
[35]  
OWRUTSKY JC, 1994, ANNU REV PHYS CHEM, V45, P519, DOI 10.1146/annurev.physchem.45.1.519
[36]   MULTIREFERENCE CONFIGURATION-INTERACTION CALCULATIONS OF THE LOW-LYING ELECTRONIC STATES OF CLO2 [J].
PETERSON, KA ;
WERNER, HJ .
JOURNAL OF CHEMICAL PHYSICS, 1992, 96 (12) :8948-8961
[37]   THE PHOTOCHEMICAL DYNAMICS OF THE A2A2 STATE OF CHLORINE DIOXIDE [J].
RICHARD, EC ;
VAIDA, V .
JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (01) :163-171
[38]   THE DIRECT NEAR ULTRAVIOLET-ABSORPTION SPECTRUM OF THE A2A2[-X2B1 TRANSITION OF JET-COOLED CHLORINE DIOXIDE [J].
RICHARD, EC ;
VAIDA, V .
JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (01) :153-162
[39]  
RUHL E, 1990, J PHYS CHEM-US, V94, P2990
[40]   CHARGE-TRANSFER SPECTRA OF HALOGEN ATOMS IN WATER - CORRELATION OF ELECTRONIC-TRANSITION ENERGIES OF IODINE, BROMINE, CHLORINE, HYDROXYL, AND HYDROGEN RADICALS WITH THEIR ELECTRON AFFINITIES [J].
TREININ, A ;
HAYON, E .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (07) :1716-1721