Theoretical study of the low‐lying electronic states of the molecular ion KRb⁺

Abstract

ABSTRACT:The potential energy curves of the molecular ion KRb ϩ have been investigated for the 60 lowest molecular states of symmetry 2 ⌺ ϩ , 2 ⌸, 2 ⌬, and ⍀ ϭ 1/2, 3/2, and 5/2. Using an ab initio method, the calculation has been done in a one active electron approach based on nonempirical pseudopotentials with core valence effects taken into account through parameterized l-dependent polarization potentials. Using the canonicals functions approach a rovibrational study is done by calculating the eigenvalues E v , the rotational constants B v , the centrifugal distortion constants D v (up to 135 vibrational levels), and the spectroscopic constants e and B e for the five electronic

Electronic transition moment with spin‐orbit coupling of the molecular ion KRb+

“…From the ab initio calculation, the potential energy curves of the molecular ion KRb ϩ have been determined within the range 3.0 a 0 Ͻ r Ͻ 50.0 a 0 and dissociating into the 12 asymptotes considered, i.e., up to 20 states of ⍀ ϭ 1/2, 12 states of ⍀ ϭ 3/2, and 4 states of ⍀ ϭ 5/2 [7]. Among these states, two are…”

“…Having the eigenvalues E v of the two states ⍀ ϭ 1/2 and ⍀ ϭ 3/2 up to v ϭ 105 [7], the pure vibrational wave function 0 and the rotational harmonics n have been calculated from Eqs. (4), (5), and (6).…”

“…Core valence effects (relativistic) have been taken into account through ᐉ-dependent core polarization potentials parameterized for each atom [2,8,10,11]. Gaussian basis sets have been used for the atoms K and Rb [7]. The spin-orbit effect has been taken into account through a semiempirical spin-orbit pseudopotential [7,12].…”

“…Gaussian basis sets have been used for the atoms K and Rb [7]. The spin-orbit effect has been taken into account through a semiempirical spin-orbit pseudopotential [7,12].…”

“…Recently [7] we investigated the potential energy curves of the molecular ion KRb ϩ for 36 lowest molecular states of symmetry ⍀ ϩ . By using these results to calculate the electronic wave functions, we investigate in this work the electronic transition moment of two bound states including the spin-orbit coupling ⍀ ϭ 1/2 and ⍀ ϭ 3/2, where the spin-orbit coupling particularly, happens to be necessary as well for qualitative interpretation as for quantitative comparison between experiment and theory.…”