Fragmentation of cyano compounds under nonlinear UV excitation: delayed CN B/sup 2/. sigma. /sup +/ chemiluminescence through ion-molecule collisions
Journal Article
·
· J. Phys. Chem.; (United States)
UV nonlinear excitation (266 nm, 4.66 eV; 22 ps) of various molecular gases may create small populations distributed over several quantum orders nhv/sub 266/, initiating distinct processes. With subnanosecond time resolution, the authors have distinguished prompt (unimolecular) and delayed (collisional) components of fragment emission in the CN violet bands, from the cyano compounds XCN (X = Cl, CN, and CH/sub 3/). A quantitative kinetic analysis of CN B/sup 2/..sigma../sup +/ ..-->.. X/sup 2/..sigma../sup +/ oscilloscope traces and comparison of the rate constants with AADO/AQO rate theory lead to the inference that the delayed emission arises through ion-molecule collisions. In our preferred picture the ions are identified as long-lived excited states of the parent species XCN/sup +/. Our previous findings with isotopically labeled CH/sub 3/CN, in particular the inference of isomerization, are quite consistent with this hypothesis. The authors suggest that similar ion-molecule channels may give rise to delayed chemiluminescence from a wide variety of simple molecules.
- Research Organization:
- Naval Research Lab., Washington, DC
- OSTI ID:
- 6800021
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:1; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
Similar Records
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MECHANISTICAL STUDIES ON THE FORMATION AND NATURE OF THE 'XCN' (OCN{sup -}) SPECIES IN INTERSTELLAR ICES
Experimental investigation of the kinetics of the B{sup 2}{Sigma}{sup +} state of CN radicals in a jet of a diaphragm-type discharge at the afterglow stage
Journal Article
·
Thu Aug 14 00:00:00 EDT 1986
· J. Phys. Chem.; (United States)
·
OSTI ID:5333340
MECHANISTICAL STUDIES ON THE FORMATION AND NATURE OF THE 'XCN' (OCN{sup -}) SPECIES IN INTERSTELLAR ICES
Journal Article
·
Mon Nov 01 00:00:00 EDT 2010
· Astrophysical Journal
·
OSTI ID:21467168
Experimental investigation of the kinetics of the B{sup 2}{Sigma}{sup +} state of CN radicals in a jet of a diaphragm-type discharge at the afterglow stage
Journal Article
·
Sat Dec 31 23:00:00 EST 1994
· Optics and Spectroscopy
·
OSTI ID:146856
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
640304 -- Atomic
Molecular & Chemical Physics-- Collision Phenomena
74 ATOMIC AND MOLECULAR PHYSICS
ALKANES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMILUMINESCENCE
CHLORINE COMPOUNDS
COLLISIONS
CYANIDES
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HYDROCARBONS
INFORMATION
ION COLLISIONS
ION-MOLECULE COLLISIONS
KINETICS
LUMINESCENCE
MOLECULE COLLISIONS
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATIONS
REACTION KINETICS
ULTRAVIOLET RADIATION
400500* -- Photochemistry
640304 -- Atomic
Molecular & Chemical Physics-- Collision Phenomena
74 ATOMIC AND MOLECULAR PHYSICS
ALKANES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMILUMINESCENCE
CHLORINE COMPOUNDS
COLLISIONS
CYANIDES
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HYDROCARBONS
INFORMATION
ION COLLISIONS
ION-MOLECULE COLLISIONS
KINETICS
LUMINESCENCE
MOLECULE COLLISIONS
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADIATIONS
REACTION KINETICS
ULTRAVIOLET RADIATION