Formation of NO3 in the Photolysis of N2O5
Abstract
The spectra of excited nitrate radicals (NO3*) produced from
the photolysis of N2O5 at 248 and 193 nm are reported for the first
time. We measured the time-resolved absorption spectra from 400
to 700 nm and separated the contributions of excited- and
ground-state species. The spectra of NO3* are broad and
featureless in this spectral region. An induction period was
observed before the formation of thermalized NO3, consistent
with the existence of NO3* that is then quenched by collisions with
the buffer gas. We re-examined the kinetics of the formation of the
room-temperature NO3 and determined the formation rate
constants in N2 at 248 and 193 nm photolysis to be (7.1±1.0)×10−13
and (7.9±1.0)×10−13 cm3molecule−1s−1, respectively. We also
measured the relative formation rate constants in O2, Ar, CO2 and
SF6 buffer gases.
the photolysis of N2O5 at 248 and 193 nm are reported for the first
time. We measured the time-resolved absorption spectra from 400
to 700 nm and separated the contributions of excited- and
ground-state species. The spectra of NO3* are broad and
featureless in this spectral region. An induction period was
observed before the formation of thermalized NO3, consistent
with the existence of NO3* that is then quenched by collisions with
the buffer gas. We re-examined the kinetics of the formation of the
room-temperature NO3 and determined the formation rate
constants in N2 at 248 and 193 nm photolysis to be (7.1±1.0)×10−13
and (7.9±1.0)×10−13 cm3molecule−1s−1, respectively. We also
measured the relative formation rate constants in O2, Ar, CO2 and
SF6 buffer gases.
Keywords
excited states, photochemistry, transient absorption, vibrational relaxation
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