We report a series of quantum-chemical calculations for the ground and some of the low-lying excited states of an isolated LiYb molecule by the spin-orbit multistate complete active space second-order perturbation theory (SO-MS-CASPT2). Potential energy curves, spectroscopic constants, and transition dipole moments (TDMs) at both spin-free and spin-orbit levels are obtained. Large spin-orbit effects especially in the TDMs of the molecular states dissociating to Yb((3)P(0,1,2)) excited states are found. To ensure the reliability of our calculations, we test five types of incremental basis sets and study their effect on the equilibrium distance and dissociation energy of the ground state. We also compare CASPT2 and CCSD(T) results for the ground state spectroscopic constants at the spin-free relativistic level. The discrepancies between the CASPT2 and CCSD(T) results are only 0.01 Å in equilibrium bond distance (R(e)) and 200 cm(-1) in dissociation energy (D(e)). Our CASPT2 calculation in the supermolecular state (R=100 a.u.) with the largest basis set reproduces experimental atomic excitation energies within 3% error. Transition dipole moments of the super molecular state (R=100 a.u.) dissociating to Li((2)P) excited states are quite close to experimental atomic TDMs as compared to the Yb((3)P) and Yb((1)P) excited states. The information obtained from this work would be useful for ultracold photoassociation experiments on LiYb.
We report a series of quantum-chemical calculations for the ground and some of the low-lying excited states of an isolated LiYb molecule by the spin-orbit multistate complete active space second-order perturbation theory (SO-MS-CASPT2). Potential energy curves, spectroscopic constants, and transition dipole moments (TDMs) at both spin-free and spin-orbit levels are obtained. Large spin-orbit effects especially in the TDMs of the molecular states dissociating to Yb((3)P(0,1,2)) excited states are found. To ensure the reliability of our calculations, we test five types of incremental basis sets and study their effect on the equilibrium distance and dissociation energy of the ground state. We also compare CASPT2 and CCSD(T) results for the ground state spectroscopic constants at the spin-free relativistic level. The discrepancies between the CASPT2 and CCSD(T) results are only 0.01 Å in equilibrium bond distance (R(e)) and 200 cm(-1) in dissociation energy (D(e)). Our CASPT2 calculation in the supermolecular state (R=100 a.u.) with the largest basis set reproduces experimental atomic excitation energies within 3% error. Transition dipole moments of the super molecular state (R=100 a.u.) dissociating to Li((2)P) excited states are quite close to experimental atomic TDMs as compared to the Yb((3)P) and Yb((1)P) excited states. The information obtained from this work would be useful for ultracold photoassociation experiments on LiYb.
We present quantum-chemical calculations for the ground and some low-lying excited states of isolated LiCa and LiSr molecules using multi-state complete active space second-order perturbation theory (MS-CASPT2). The potential energy curves (PECs) and their corresponding spectroscopic constants, obtained at the spin-free (SF) and spin-orbit (SO) levels, agree well with available experimental values. Our SO-MS-CASPT2 calculation at the atomic limit (R = 100 a.u.) with the largest basis set reproduces experimental atomic excitation energies within 3% for both LiCa and LiSr. In addition, permanent dipole moments and transition dipole moments at the SF level are also obtained. Rovibrational calculations of the ground and selected excited states, together with the spontaneous emission rates, demonstrate that the formation of ultracold LiCa and LiSr molecules in low-lying vibrational levels of the electronic ground state may be possible.
In this work, we present a thorough theoretical structure and spectroscopic study of the ground and low lying excited states of RbBa molecule. High-level ab-initio calculations are performed, using MCSCF/MRCI+Q level of method, based on the effective core potential (ECP) and core-polarization potential (CPP) approach. The potential energy curves, spectroscopic parameters, vibrationnel energy levels of the 16( 2,4 Σ + , 2,4 Π, 2,4 Δ) first electronic states, with respect to the lowest five dissociation limits were calculated. The comparison of the spectroscopic constants of the ground state X 2 Σ + with the available theoretical work, are in good agreement. The study of all the excited states is performed in this work for the first time. Afterwards, the spin-orbit operator is incorporated in valence MRCI calculation using optimized relativistic spin-orbit pseudo-potentials and 33 Ω states are generated and split into Λ-S states. In addition, both relativistic and non relativistic calculations of permanent and transition dipole moments are presented and discussed. Stimulated black body ( T = 300 K) and spontaneous transition rates of vibrational states of X 2 Σ + state were evaluated. The related vibrational lifetimes for RbBa are found to be in order of 10 3 s which is sufficiently large for ultracold experiments. Moreover, the vibrational life-time for the A 2 Σ + ( v’ ) and A 2 П ( v” ) states are measured and the possibility of Laser Cooling for the RbBa molecule is discussed based on Franck–Condon factors calculation of A 2 Σ + ( v’ )→ X 2 Σ + ( v ) and A 2 П( v” ) → X 2 Σ + ( v ) transition. This work represents a significant contribution for experimentalists as it provides efficient information in order to form cold alkali and alkaline-earth RbBa molecules.
Ab initio techniques have been applied to investigate the electronic structure of the LiYb molecule. The potential energy curves have been computed in the Born-Oppenheimer approximation for the ground and 29 low-lying doublet and quartet excited electronic states. Complete active space self-consistent field, multi-reference configuration interaction, and Rayleigh Schrödinger perturbation theory to second order calculations have been utilized to investigate these states. The spectroscopic constants, ωe, Re, Be, …, and the static dipole moment, μ, have been investigated by using the two different techniques of calculation with five different types of basis. The eigenvalues, Ev, the rotational constant, Bv, the centrifugal distortion constant, Dv, and the abscissas of the turning points, Rmin and Rmax, have been calculated by using the canonical functions approach. The comparison between the values of the present work, calculated by different techniques, and those available in the literature for several electronic states shows a very good agreement. Twenty-one new electronic states have been studied here for the first time.
The accurate knowledge of electronic properties is important for creating and manufacturing ultracold molecules. We report here the ab initio quantum chemistry calculations on the properties of alkali-metal-ytterbium AM-Yb (AM = Li, Na, K, Rb, Cs) and alkaline-earth-metal-ytterbium AEM-Yb (AEM = Be, Mg, Ca, Sr, Ba) molecules for their electronic ground state. The potential energy curves (PECs) and permanent dipole moments (PDMs) are calculated on the basis of the multireference configuration interaction (MRCI) level of theory, where the core-valence correlations and scalar relativistic effects are included. The related spectroscopic constants are also determined. The results demonstrate that the dissociation energies and PDMs of AEM-Yb are smaller than those of AM-Yb molecules, and an interesting trend of the dissociation energy has been observed. This work provides favorable information for the experimental study of forming ultracold molecules via photoassociation technique.
State-of-the-art ab initio techniques have been applied to compute the potential energy curves for the SrYb molecule in the Born-Oppenheimer approximation for the electronic ground state and the first fifteen excited singlet and triplet states. All the excited state potential energy curves were computed using the equation of motion approach within the coupled-cluster singles and doubles framework and large basis-sets, while the ground state potential was computed using the coupled cluster method with single, double, and noniterative triple excitations. The leading long-range coefficients describing the dispersion interactions at large interatomic distances are also reported. The electric transition dipole moments have been obtained as the first residue of the polarization propagator computed with the linear response coupled-cluster method restricted to single and double excitations. Spin-orbit coupling matrix elements have been evaluated using the multireference configuration interaction method restricted to single and double excitations with a large active space. The electronic structure data were employed to investigate the possibility of forming deeply bound ultracold SrYb molecules in an optical lattice in a photoassociation experiment using continuous-wave lasers. Photoassociation near the intercombination line transition of atomic strontium into the vibrational levels of the strongly spin-orbit mixed b(3)Σ(+), a(3)Π, A(1)Π, and C(1)Π states with subsequent efficient stabilization into the v'' = 1 vibrational level of the electronic ground state is proposed. Ground state SrYb molecules can be accumulated by making use of collisional decay from v'' = 1 to v'' = 0. Alternatively, photoassociation and stabilization to v'' = 0 can proceed via stimulated Raman adiabatic passage provided that the trapping frequency of the optical lattice is large enough and phase coherence between the pulses can be maintained over at least tens of microseconds.
We perform a systematic investigation of the electronic properties of the (2)Σ(+) ground state of Li-alkaline-earth dimers. These molecules are proposed as possible candidates for quantum simulation of lattice-spin models. We apply powerful quantum chemistry coupled-cluster method and large basis sets to calculate potential energies and permanent dipole moments for the LiBe, LiMg, LiCa, LiSr, and LiYb molecules. Agreement of calculated molecular constants with existing experimental data is better than or equal to 8%. Our results reveal a surprising irregularity in the dissociation energy and bond length with an increase in the reduced mass of the molecule. At the same time, the permanent dipole moment at the equilibrium separation has the smallest value between 0.01 a.u. and 0.1 a.u. for the heaviest (LiSr and LiYb) molecules and increases to 1.4 a.u. for the lightest (LiBe), where 1 a.u. is one atomic unit of dipole moment. We consider our study of the (2)Σ(+) molecules a first step towards a comprehensive analysis of their interactions in an optical trap.