Ab initio calculations of permanent dipole moments and dipole polarizabilities of alkaline-earth monofluorides

Abstract

The ground -state permanent dipole moments (PDMs) and molecular dipole polarizabilities (DPs) of open-shell alkaline-earth monofluorides, and atomic DPs of alkaline -earth-and fluorine atoms are reported at the Kramers -restricted configuration interaction level of theory limited to single and double excitations (KRCISD), using the finite -field approach. Sufficiently large basis sets such as quadrupole -zeta (QZ) and augmented -QZ basis sets together with the generalized active space technique is employed to carry out the field dependent energy calculations at the KRCISD level. The PDMs and the components of DPs are extracted from the linear-and quadratic fit of energies against perturbative electric field, respectively. Accuracy of the present calculations for the electronic properties is examined by comparison with the measurements and calculations where ever available.

Molecular frame dipole moment of diatomic molecules within relativistic coupled‐cluster framework: A comparative study of expectation value versus energy derivative approach

“…Also, the relativistic effect becomes more pronounced for heavier systems. It has been reported in earlier work [20] that the difference in the PDM obtained from relativistic and non-relativistic calculation, increases due to the increase in relativistic effects, as one goes from lighter to heavier molecules.…”

“…In this paper our main concern is to compare the results obtained from LEV method and Z-vector method using same basis and correlation space. A detailed compilation of previously obtained results using several basis sets can be found in Bala et al [20] and Prasannaa et al [19].…”

“…PDMs of BeF, MgF and CaF were calculated using the second order Moller-Plesset perturbation (MP2) theory by Buckingham et al [15] All the above mentioned semi-empirical and ab initio calculations of PDM were performed in a nonrelativistic framework. However, from several previous investigations carried out by different groups [16][17][18][19][20] it has now been established that PDM is largely affected by the spin-orbit coupling effects along with the electron correlation in a molecule, especially for the heavy ones. Therefore, a suitable theoretical method for accurate calculation of PDM would be the one which can capture the interplay of relativistic and correlation effects correctly.…”

“…They also calculated the PDM of RaF using the same method [30]. Theoretical investigations of the ground and lowest excited states of BaF and its lighter homologs were carried out in a relativistic Fock-space CC method by Hao et al [31] Most recently Bala et al [20] have reported the PDMs of alkaline earth metal monofluorides (AEMF) at the Kramers-restricted CI level of theory limited to the single and double excitations (KRCISD).…”

Calculations of $\mathcal{P}$ and $\mathcal{T}$-odd interaction constants of alkaline-earth monofluorides using KRCI method

“…Heavier members of this series, particularly BaF and RaF, have been studied for the nuclear anapole moment [24][25][26][27], another parity-violating effect. The theoretical as well as experimental results of spectroscopic constants, valence properties and vibrational parameters for the ground -and excited states of AEMFs have also been reported by several research groups [26,[28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45]. Nevertheless, there is a scope to carry out the calculations of P & T -odd interaction constants of these molecules consistently employing accurate many-body methods as there are only a very few calculations available in the literature.…”