skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Accurate ab initio calculations of radiative transition probabilities between the A /sup 3/. sigma. /sup +//sub u/, B /sup 3/Pi/sub g/, W /sup 3/. delta. /sub u/, B' /sup 3/. sigma. /sup -//sub u/, and C /sup 3/Pi/sub u/ states of

Abstract

Potential energy and electronic transition moment functions for the lowest five triplet states of N/sub 2/ have been calculated from highly correlated multiconfiguration-reference CI wave functions. From the calculated transition moments and RKR potential energy functions, radiative transition probabilities and lifetimes have been evaluated which are believed to be accurate within 15%. The theoretical lifetime of 36.7 ns of the C /sup 3/Pi/sub u/ state is in close agreement with the most recent experimental values. The calculated lifetimes of the B /sup 3/Pi/sub g/ state decrease from 13.4 ..mu..s for v' = 0 to 4.82 ..mu..s for v' = 12. The values for v' = 5 to v' = 12 are in good agreement with recent LIF measurements. The lifetimes for v' = 0 to v' = 4, however, are considerably larger than most previously measured values. The fact that the calculated values are very stable with respect to improvements of the electronic wave functions leads us to conclude that the experimental values are too low. Empirical transition moment functions for the B--A system are apparently too steep, and the moments at short distances much too large. Previous estimates of the lifetimes of the W /sup 3/..delta../sub u/ vibrational levelsmore » are three times smaller than our calculated values, whereas estimates for the B /sup 3/..sigma../sup -//sub u/ state agree reasonably well with the theoretical results.« less

Authors:
; ;
Publication Date:
Research Org.:
Los Alamos National Laboratory, Los Alamos, New Mexico 84575
OSTI Identifier:
6572142
Resource Type:
Journal Article
Journal Name:
J. Chem. Phys.; (United States)
Additional Journal Information:
Journal Volume: 81:5
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; NITROGEN; ELECTRONIC STRUCTURE; ENERGY-LEVEL TRANSITIONS; CONFIGURATION INTERACTION; PROBABILITY; ELEMENTS; NONMETALS; 640302* - Atomic, Molecular & Chemical Physics- Atomic & Molecular Properties & Theory

Citation Formats

Werner, H, Kalcher, J, and Reinsch, E. Accurate ab initio calculations of radiative transition probabilities between the A /sup 3/. sigma. /sup +//sub u/, B /sup 3/Pi/sub g/, W /sup 3/. delta. /sub u/, B' /sup 3/. sigma. /sup -//sub u/, and C /sup 3/Pi/sub u/ states of. United States: N. p., 1984. Web.
Werner, H, Kalcher, J, & Reinsch, E. Accurate ab initio calculations of radiative transition probabilities between the A /sup 3/. sigma. /sup +//sub u/, B /sup 3/Pi/sub g/, W /sup 3/. delta. /sub u/, B' /sup 3/. sigma. /sup -//sub u/, and C /sup 3/Pi/sub u/ states of. United States.
Werner, H, Kalcher, J, and Reinsch, E. Sat . "Accurate ab initio calculations of radiative transition probabilities between the A /sup 3/. sigma. /sup +//sub u/, B /sup 3/Pi/sub g/, W /sup 3/. delta. /sub u/, B' /sup 3/. sigma. /sup -//sub u/, and C /sup 3/Pi/sub u/ states of". United States.
@article{osti_6572142,
title = {Accurate ab initio calculations of radiative transition probabilities between the A /sup 3/. sigma. /sup +//sub u/, B /sup 3/Pi/sub g/, W /sup 3/. delta. /sub u/, B' /sup 3/. sigma. /sup -//sub u/, and C /sup 3/Pi/sub u/ states of},
author = {Werner, H and Kalcher, J and Reinsch, E},
abstractNote = {Potential energy and electronic transition moment functions for the lowest five triplet states of N/sub 2/ have been calculated from highly correlated multiconfiguration-reference CI wave functions. From the calculated transition moments and RKR potential energy functions, radiative transition probabilities and lifetimes have been evaluated which are believed to be accurate within 15%. The theoretical lifetime of 36.7 ns of the C /sup 3/Pi/sub u/ state is in close agreement with the most recent experimental values. The calculated lifetimes of the B /sup 3/Pi/sub g/ state decrease from 13.4 ..mu..s for v' = 0 to 4.82 ..mu..s for v' = 12. The values for v' = 5 to v' = 12 are in good agreement with recent LIF measurements. The lifetimes for v' = 0 to v' = 4, however, are considerably larger than most previously measured values. The fact that the calculated values are very stable with respect to improvements of the electronic wave functions leads us to conclude that the experimental values are too low. Empirical transition moment functions for the B--A system are apparently too steep, and the moments at short distances much too large. Previous estimates of the lifetimes of the W /sup 3/..delta../sub u/ vibrational levels are three times smaller than our calculated values, whereas estimates for the B /sup 3/..sigma../sup -//sub u/ state agree reasonably well with the theoretical results.},
doi = {},
url = {https://www.osti.gov/biblio/6572142}, journal = {J. Chem. Phys.; (United States)},
number = ,
volume = 81:5,
place = {United States},
year = {1984},
month = {9}
}