Determination of the Optimal Energy Denominator Shift Parameter of KRb Electronic States in Quantum Chemical Computations Using Perturbation Theory

Min'ko

2017

The potential energy curves of the ground and twelve low-lying excited electronic states of the RbYb molecule have been calculated using the multi-reference perturbation theory method at the CASSCF/ XMCQDPT2 level of theory including the spin-orbit coupling. The electronic term energies, equilibrium internuclear distances, dissociation energies, transition dipole moments, the sequences of vibrational energies, the harmonic vibrational frequencies, and the Franck-Condon factors have been predicted. The potential energy curves at the asymptotic limits are in a good agreement with the experimental data for rubidium and ytterbium atoms. The obtained data would be useful for spectral experiments with RbYb molecules.

Section: Electronic Statesmentioning

confidence: 60%

Section: Introductionmentioning

confidence: 99%

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Ab initio multi-reference perturbation theory calculations of the ground and some excited electronic states of the RbYb molecule

Min'ko

2017

“…To obtain more reliable energies XMCQDPT2 method [16] was used. All the eight lowest double occupied orbitals were involved in the perturbation calculations, the ISA shift [21] of 0.190 [22] being used. The dimensions of the effective Hamiltonian were 11 Â 11 and 5 Â 5 for doublet and quartet states, respectively.…”

Section: Computationsmentioning

confidence: 99%

Multi-reference perturbation theory study on the CsYb molecule including the spin-orbit coupling

Meniailava

2017

We present CASSCF/XMCQDPT2 level of theory calculations of the ground and sixteen low-lying excited electronic states of the CsYb molecule taking into account the spin-orbit coupling. Spectroscopic constants (electronic term energies, equilibrium internuclear distances, dissociation energies, harmonic vibrational frequencies), transition dipole moments, Franck-Condon factors and vibrational energies of the CsYb molecule have been obtained. The energies of the ground and first exited states at the asymptotic limits definitely satisfy the experimental data for cesium and ytterbium atoms. All the data obtained allow to predict and realize two-photon schemes for producing ultracold CsYb molecules and carry out spectral experiments with them.

“…All eight lowest double occupied orbitals were included in the perturbation based calculations. The ISA shift of 0.20 [47,48] was used in present approach. The dimension of the effective Hamiltonian was 13 Â 13 [48].…”

Section: Computationsmentioning

confidence: 99%

Ab initio multi-reference perturbation theory calculations of the ground and low-lying electronic states of the KRb molecule

Pitsevich

Malevich

et al. 2016

The potential energy curves of the low-lying electronic states correlating up to the limit K(4p) + Rb(5s) of KRb molecule have been calculated using the multi-reference perturbation theory method at the CASSCF/ XMCQDPT2 level of theory without and with spin-orbit coupling. The calculated parameters of the ground X 1 R + state are in the best agreement among all previously performed ab initio calculations for the KRb molecule. The calculated vibrational intervals of the ground electronic term of the 39 K 85 Rb molecule describe the experiment with the accuracy within ±1 cm À1 . The calculated intensities of the 2 1 R + (v 0 = 3, J 0 = 26) ? X 1 R + (v 00 = 0. . .24, J 00 = 25, 27) transitions satisfactory reflect the experimentally observed intensities distribution.