Internal energy distributions from nitrogen dioxide fluorescence. 4. Variable-wavelength photodissociation of ClNO[sub 2] and HONO[sub 2]

Journal Article · Thu Sep 30 00:00:00 EDT 1993 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100141a007· OSTI ID:5651592

Miller, C E; Johnston, H S ^[1]

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1. Univ. of California, Berkeley, CA (United States) Lawrence Berkeley Lab., CA (United States)

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.

• DOE Contract Number: AC03-76SF00098
• OSTI ID: 5651592
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 97:39; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 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
400201* - Chemical & Physicochemical Properties
400500 - Photochemistry