Abstract
The potential energy and dipole moment curves for the lowest electronic states in the representation 2s+1Λ(±) of CdX (X = F, Cl, Br, I) molecules are investigated via complete active space self-consistent field (CASSCF) and multi-reference configuration interaction MRCI (single and double excitation with Davidson correction). For the bound states of CdX diatomic molecules the bond distances Re, the vibrational harmonic frequencies ωe, the rotational constants Be, the electronic energies relative to the ground state Te, and the permanent and transition dipole moments have been computed. The dissociation energy limits of the atomic levels of CdX compounds are also calculated. The transition dipole moment between the ground state X2Σ+ and (2)2Σ+ is investigated. Consequently, the transition dipole moment values of the upper state at its equilibrium position μ21, the emission angular frequency ω21, the Einstein coefficients of spontaneous and induced emissions (A21 and B21ω), the spontaneous radiative lifetime τspon, the emission cross section σ0, the line strength and the emission oscillator strength f21 are calculated along with the ionicity of the X2Σ+ and (2)2Σ+ states. The eigenvalues Ev, the rotational constants Bv, the centrifugal distortion constants Dv and the abscissas of the turning points Rmin and Rmax of X2Σ+ states of the CdX diatomics are computed. The comparison of the results with those available in literature shows a very good agreement.
Highlights
The ab initio calculation of molecular properties associated with the electronic transitions of diatomic molecules has become an important partner in the interpretation of spectra
State averaged complete active space self-consistent field (SA-CASSCF) calculations[36] have been carried out with valence active molecular orbitals to represent the wavefunction of the outer electrons of the low lying electronic states of cadmium monohalides CdX (X = F, Cl, Br, I) in their neutral state
For Cd atom, the 28 inner electrons are replaced by the effective core potential (ECP), while the remaining 20 electrons are treated as active ones
Summary
The ab initio calculation of molecular properties associated with the electronic transitions of diatomic molecules has become an important partner in the interpretation of spectra. The ab initio calculations of these diatomic molecule can achieve spectroscopic accuracy along with reliable picture for the electronic structure Such information is an invaluable guide to the interpretation of observed spectra and as a supplement to measurements when no other information is available.[1,2] The investigation of electronic structure of transition metal monohalides is of great interest in many fields ranging from high-temperature chemistry to catalysts. Based on the MRCI +Q technique, Zhao et al.[33] examined the spectroscopic parameters of nine Λ–S electronic states including the ground state Both experimental and theoretical investigations are available in the literature for the neutral CdBr and CdI. The eigenvalues Ev, the rotational constants Bv, the centrifugal distortion constants Dv and the abscissas of the turning points Rmin and Rmax of X2Σ+ of the CdX diatomic are computed
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