Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

On the electronic structure aspects of spin-forbidden processes in N[sub 2]O

Journal Article · · Journal of Chemical Physics; (United States)
DOI:https://doi.org/10.1063/1.465826· OSTI ID:5903934
;  [1]
  1. Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218 (United States)
+ Show Author Affiliations
The crossing surfaces corresponding to the intersection of the lowest singlet surface of N[sub 2]O and the three triplet surfaces correlating with N[sub 2]+O([sup 3][ital P]) are studied using multireference configuration interaction wave functions comprised principally of 300 000--500 000 terms, but with some calculations using expansions as large as 1 700 000 terms. These (1 [sup 1][ital A][prime],1 [sup 3][ital A][prime]), (1 [sup 1][ital A][prime],1 [sup 3][ital A][double prime]), and (1 [sup 1][ital A][prime],2 [sup 3][ital A][double prime]) crossing surfaces are characterized in the vicinity of their minimum energy points. The minimum energy crossing structures are each linear and correspond to ([ital X] [sup 1][Sigma][sup +],[sup 3][Pi]) and ([ital X] [sup 1][Sigma][sup +],[sup 3][Sigma][sup [minus]]) intersections. The minimum energy point on ([ital X] [sup 1][Sigma][sup +],[sup 3][Pi]) crossing surface, was found to be [similar to]58 kcal/mol above the N[sub 2]O([ital X] [sup 1][Sigma][sup +]) minimum. The minimum energy point on ([ital X] [sup 1][Sigma][sup +],[sup 3][Sigma][sup [minus]]) crossing surface was found to be 71 kcal/mol above the N[sub 2]O([ital X] [sup 1][Sigma][sup +]) minimum. The N--N bond distance is similar at the ([ital X] [sup 1][Sigma][sup +],[sup 3][Pi]) and ([ital X] [sup 1][Sigma][sup +],[sup 3][Sigma][sup [minus]]) minimum energy crossing structures, being 1.116 and 1.113 A, respectively, and approximately equal to that in isolated N[sub 2]([ital X] [sup 1][Sigma][sub [ital g]][sup +]). The N--O bond is 1.72 and 1.96 A for the ([ital X] [sup 1][Sigma][sup +],[sup 3][Pi]) and ([ital X] [sup 1][Sigma][sup +],[sup 3][Sigma][sup [minus]]) minimum energy crossing structures, respectively, and significantly stretched when compared with its value, 1.18 A, at the equilibrium geometry of N[sub 2]O([ital X] [sup 1][Sigma][sup +]).
DOE Contract Number:
FG02-91ER14189
OSTI ID:
5903934
Journal Information:
Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 99:9; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English

Similar Records

Electronic structure aspects of the spin-forbidden reaction CH{sub 3}(X{sup 2}A{sub 2}{sup {double_prime}})+N({sup 4}S){r_arrow}HCN(X{sup 1}{Sigma}{sup +})+H{sub 2}(X{sup 1}{Sigma}{sub g}{sup +})
Journal Article · Wed Oct 01 00:00:00 EDT 1997 · Journal of Chemical Physics · OSTI ID:542173
Theoretical studies of spin-forbidden radiationless decay in polyatomic systems: Insights from recently developed computational methods
Journal Article · Wed Jun 17 00:00:00 EDT 1992 · Journal of the American Chemical Society · OSTI ID:284996
Product branching fractions in the reaction of NH (ND) ([sup 3][Sigma][sup [minus]]) with NO
Journal Article · Wed Jan 12 23:00:00 EST 1994 · Journal of Physical Chemistry; (United States) · OSTI ID:5153714

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
664100 -- Theory of Electronic Structure of Atoms & Molecules-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
ATOM COLLISIONS
ATOM-MOLECULE COLLISIONS
CHALCOGENIDES
CHEMICAL REACTIONS
COLLISIONS
CONFIGURATION INTERACTION
COUPLING
EARTH ATMOSPHERE
ELECTRONIC STRUCTURE
ELEMENTS
ENERGY LEVELS
FUNCTIONS
HYDROXYL RADICALS
INTERMEDIATE COUPLING
L-S COUPLING
MOLECULE COLLISIONS
NITROGEN
NITROGEN COMPOUNDS
NITROGEN OXIDES
NITROUS OXIDE
NONMETALS
OXIDES
OXYGEN
OXYGEN COMPOUNDS
RADICALS
WAVE FUNCTIONS