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Author Miller, C. E. ♦ Johnston, H. S.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ NITROGEN DIOXIDE ♦ FLUORESCENCE SPECTROSCOPY ♦ CHLORINE COMPOUNDS ♦ DISSOCIATION ♦ ENERGY TRANSFER ♦ EXCITED STATES ♦ FLUORESCENCE ♦ HYDROXY COMPOUNDS ♦ LEAST SQUARE FIT ♦ MATRICES ♦ PHOTOLYSIS ♦ TIME-OF-FLIGHT METHOD ♦ VIBRATIONAL STATES ♦ CHALCOGENIDES ♦ CHEMICAL REACTIONS ♦ DECOMPOSITION ♦ EMISSION SPECTROSCOPY ♦ ENERGY LEVELS ♦ HALOGEN COMPOUNDS ♦ LUMINESCENCE ♦ MAXIMUM-LIKELIHOOD FIT ♦ NITROGEN COMPOUNDS ♦ NITROGEN OXIDES ♦ NUMERICAL SOLUTION ♦ ORGANIC COMPOUNDS ♦ OXIDES ♦ OXYGEN COMPOUNDS ♦ PHOTOCHEMICAL REACTIONS ♦ SPECTROSCOPY ♦ Chemical & Physicochemical Properties ♦ Photochemistry
Abstract The cumulative sum spectroscopy method is used to derive internal energy distributions for the fluorescing NO[sub 2] ensembles from ClNO[sub 2] and HONO[sub 2] photodissociations as a function of the photolysis wavelength. The fluorescing NO[sub 2] ensemble internal energy distribution, NO[sub 2]* P(E[sub int]), for ClNO[sub 2] evolves from distributions peaked at 25 130 cm[sup [minus]1] to those having a majority of the NO[sub 2]* components with internal energies less than 15 000 cm[sup [minus]1] as the energy available to the photofragments decreases from 30 000 to 20 000 cm[sup [minus]1]. The NO[sub 2]* P(E[sub int]) distributions derived for HONO[sub 2] are dominated by components with energies less than 15 000 cm[sup [minus]1], and only for photolysis wavelength shorter than 255 nm do the distributions have significant contributions from NO[sub 2]* components approaching the maximum available energy. The PIF P(E[sub int]) derived from 308-nm ClNO[sub 2] photodissociation is compared to the P(E[sub T]) distribution derived from time-of-flight experiments, and the HONO[sub 2] PIF P(E[sub int]) distributions are compared to energy-partitioning measurements made after 241- and 280-nm photolysis. 19 refs., 20 figs.
ISSN 00223654
Educational Use Research
Learning Resource Type Article
Publisher Date 1993-09-30
Publisher Place United States
Journal Journal of Physical Chemistry
Volume Number 97
Issue Number 39


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