Direct deperturbation analysis of the A(2)Pi ∼ B(2)Sigma(+) complex of (LiAr)-Li-7,6 isotopomersстатья
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Аннотация:Direct deperturbation analysis of the highly accurate experimental
rovibronic term values of the A (2)Pi similar to B (2)Sigma(+) complex
of LiAr {[}R. Bruhl and D. Zimmermann, J. Chem. Phys. 114, 3035 (2001)]
has been performed in the framework of inverted close-coupling approach
implicitly adjusted to the unified treatment of the overall A similar to
B coupling effect without reducing the rovibrational dimensionality. The
nonlinear fitting procedure was supported by the ab initio calculations
on the spin-orbit and angular coupling matrix elements between the
lowest X (2)Sigma(+), A (2)Pi, and B (2)Sigma(+) states. The analytical
grid mapping based on the reduced variable representation of the radial
coordinate r was used to improve the efficiency of the solution of the
close-coupling radial equations near the dissociation limit. The mutual
A similar to X perturbation effect on the A (2)Pi term values and
spin-rotation splitting of the ground state were evaluated for both
(LiAr)-Li-7,6 isotopomers. The resulting empirical potential-energy
curves for the adiabatic A (2)Pi and B (2)Sigma(+) states, along with
the refined r-dependent nonadiabatic matrix elements, reproduce the
total rovibronic structure of the (LiAr)-Li-7 complex with the standard
deviation of 0.003 cm(-1). The mass invariance of the deperturbed
electronic parameters was confirmed by the calculation of the rovibronic
term values of the (LiAr)-Li-6 isotopomer which coincided with their
experimental counterparts within 0.004 cm(-1).