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
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.