PERTURBATION AND PREDISSOCIATION NEAR THE DISSOCIATION LIMIT OF THE B-1-PI STATE OF (NAK)-NA-23-K-39

Citation
S. Kasahara et al., PERTURBATION AND PREDISSOCIATION NEAR THE DISSOCIATION LIMIT OF THE B-1-PI STATE OF (NAK)-NA-23-K-39, The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 101(4), 1997, pp. 422-428
Citations number
19
Categorie Soggetti
Chemistry Physical
ISSN journal
10895639
Volume
101
Issue
4
Year of publication
1997
Pages
422 - 428
Database
ISI
SICI code
1089-5639(1997)101:4<422:PAPNTD>2.0.ZU;2-U
Abstract
The J' dependencies of energy and line width of the (NaK)-Na-23-K-39 B -1 Pi(upsilon' = 30-43, J') <-- X(1) Sigma(+)(upsilon'' = 2, J') trans itions are measured up to the breaking-off points, where NaK dissociat es to the Na(3s(2)S(1/2)) + K(4p(2)P(3/2)) atoms. Line broadenings are observed for transitions to the B-1 Pi(upsilon' = 30, J' greater than or equal to 42), (upsilon' = 31, J'greater than or equal to 35), (ups ilon' = 32, J' greater than or equal to 27), (upsilon' = 33, J' greate r than or equal to 14), and (upsilon' greater than or equal to 34, all J') levels, and are attributed to the predissociation via the c(3) Si gma(+) state to the Na(3s(2)S(1/2)) + K(4p(2)P(1/2)) atoms. The (upsil on', J') dependence of the predissociation threshold is attributed to the potential barrier due to rotation. Below and near the threshold, a series of the perturbation centers which converge to the predissociat ion threshold is observed for each upsilon', and the perturbing state is identified as the c(3) Sigma(+) state. Rotational perturbations are observed also above the predissociation threshold, and the perturbing state is identified as the b3 Pi(1) state. The line widths are observ ed to change drastically around the maximum perturbation, and this is identified as originating from the interference effect which arises be cause both the B-1 Pi and b(3) Pi(1) states interact with the dissocia tive continuum of the c(3) Sigma(+) state. In the transitions to level s near the breaking-off points of the B-1 Pi(upsilon' greater than or equal to 37), the line splittings into two lines are observed for each J'. This splitting is identified as originating from the S-uncoupling interaction between the B-1 Pi and b(3) Pi states at a long internucl ear distance. Similar line splittings an observed for the B-1 Pi(upsil on' = 30, all J') levels, but are not observed for upsilon' = 31-36. A n accidental coincidence of the level energies of the B-1 Pi(upsilon' = 30) and b(3) Pi(upsilon) levels is presumed, and the origin of the l ine splitting is identified as the S-uncoupling interaction. This is c onfirmed by the analysis of the hyperfine structures observed for the split lines.