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Femtosecond pump-probe studies of actinic-wavelength dependence in aqueous chlorine dioxide photochemistry
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10.1063/1.3116108
/content/aip/journal/jcp/130/15/10.1063/1.3116108
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/15/10.1063/1.3116108

Figures

Image of FIG. 1.
FIG. 1.

Potential energy surfaces for OClO as a function of distortion along asymmetric-stretch coordinate. Figure is adapted from the theoretical calculations of Peterson and Werner (Ref. 28). The ground state , optically prepared excited state , and lower energy excited states ( and ) are shown.

Image of FIG. 2.
FIG. 2.

The absorption spectra of OClO (aq) (solid line), ClOO (s) (dashed line) (Ref. 9), ClO (aq) (closed circle) (Ref. 38), and the charge-transfer complex (open circle) (Ref. 39).

Image of FIG. 3.
FIG. 3.

Evolution in optical density for aqueous OClO following 310 nm photoexcitation. Probe wavelengths and the optical-density scale are indicated. Circles represent the experimentally observed optical-density evolution. The solid lines represent the best fit to the data for each probe wavelength by a sum of exponentials. Fit parameters are presented in Table I.

Image of FIG. 4.
FIG. 4.

Evolution in optical density for aqueous OClO following 335 nm photoexcitation. Probe wavelengths and the optical-density scale are indicated. Circles represent the experimentally observed optical-density evolution. The solid lines represent the best fit to the data for each probe wavelength by a sum of exponentials. Fit parameters are presented in Table II.

Image of FIG. 5.
FIG. 5.

Evolution in optical density for aqueous OClO (aq) following 410 nm photoexcitation. Probe wavelengths and the optical-density scale are indicated. Circles represent the experimentally observed optical-density evolution. The solid lines represent the best fit to the data for each probe wavelength by a sum of exponentials. Fit parameters are presented in Table III.

Image of FIG. 6.
FIG. 6.

Long-time evolution in optical density for aqueous OClO with excitation at of 410, 335, and 310 nm. Probe wavelengths, the optical-density scale are indicated. Circles represent the experimentally observed changed in optical density. The solid lines represent the best fit for each probe wavelength by a sum of exponentials with fit parameters provided in Sec. III and Tables I–III.

Image of FIG. 7.
FIG. 7.

Actinic energy dependence of OClO dissolved in water. OClO geminate recombination quantum yield (filled circle) and chlorine quantum yield (filled triangle) are depicted at the three photolysis wavelengths employed in this study.

Tables

Generic image for table
Table I.

Kinetic parameters determined from the time resolved pump-probe studies of OClO(aq) at 310 nm photoexcitation.

Generic image for table
Table II.

Kinetic parameters determined from the time resolved pump-probe studies of OClO(aq) at 335 nm photoexcitation.

Generic image for table
Table III.

Kinetic parameters determined from the time resolved pump-probe studies of OClO(aq) at 410 nm photoexcitation.

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/content/aip/journal/jcp/130/15/10.1063/1.3116108
2009-04-15
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Femtosecond pump-probe studies of actinic-wavelength dependence in aqueous chlorine dioxide photochemistry
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/15/10.1063/1.3116108
10.1063/1.3116108
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