Theoretical electronic structure with rovibrational calculations of the alkali chloride molecules XCl (X = Li, Na, K, Rb, Cs)

Abstract

The adiabatic potential energy curves and the static dipole moment curves of the low-lying singlet and triplet electronic states in the representation 2s+1Λ(+/−) of the five alkali chloride molecules (LiCl, NaCl, KCl, RbCl and CsCl) have been investigated via ab initio calculations using the state averaged complete active space self consistent field followed by the Multi-reference single and double configuration interaction method with Davidson correction CASSCF/(MRCI + Q). For the molecules under consideration, the spectroscopic constants Te, Re, ωe and Be, the dipole moment μe, and the dissociation energy De have been calculated for the bound states along with the percentage ionic character fionic around the equilibrium position of the ground state. Moreover, the transition dipole moment curves of the X1∑+–(2)1∑+ and X1∑+–(1)1Π transitions have been investigated for the five alkali chloride molecules. A rovibrational calculation was carried out using the canonical functions approach in order to determine the rovibrational constants Ev, Bv and Dv and the abscissas of the turning points Rmin and Rmax for the investigated bound states.

Theoretical electronic structure with rovibrational calculations of alkali-beryllium molecules BeX (X = K, Rb, Cs)

“…ECP 28MWB for s and p was used for Rb in [26]. As much as Rb and Cs are treated respectively in ECP 28MWB and ECP 46MWB [17,27]. Moreover, choosing other basis sets rather than ECP for (K, Rb and Cs) would be time consuming since large number of electrons would be considered, noticing that our results have very good agreement with those published in literature.…”

A theoretical electronic structure with a feasibility study of laser cooling of LaNa molecules with a spin orbit effect

“…By interpolating the PECs between each of the two consecutive points and using the canonical functions approach, [40][41][42] the rovibrational parameters such as the vibrational energy E n , the rotational constant B n , the centrifugal distortion constant D n , and the abscissas of turning points R min and R max are calculated for the lowest vibrational levels of the spin-free states X 1 S + , 1 1 P, 1 1 D, 1 3 P, 1 3 D and 1 3 S + investigated in the L-S representation and the spin-orbit O states (1)0 + and (1)1. The parameters of the (1)0 + and (1)1 states and the ground state X 1 S + , 1 1 P, 1 1 D, 1 3 P, 1 3 D and 1 3 S + are given in Tables S4-S8 in the ESI † for the lowest vibrational levels.…”

A spin–orbit configuration interaction study of the low-lying electronic states of the diatomic lithium antimonide cation

“…With regard to diatomic lithium-containing species, in the last 30 years, investigations have been carried out to determine the molecular structures and spectroscopic properties of Li 2 [52][53][54], LiBe [55][56][57], LiB [58][59][60][61][62], LiC [63][64][65][66], LiN [67,68], LiO [69,70], LiF [71], LiNa [52,53,[72][73][74], LiMg [75][76][77][78][79], LiAl [80][81][82][83], LiSi [65], LiP [68,[84][85][86], LiS [87][88][89][90], LiCl [91,92], LiGa [93], LiGe [65], LiAs [94], LiSn [65], LiSb …”