Rovibrational dynamics of the strontium molecule in the A1Σu+, c3Πu, and a3Σu+ manifold from state-of-the-art ab initio calculations

Quantum Chemistry Laboratory, Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland.
The Journal of Chemical Physics (Impact Factor: 2.95). 05/2012; 136(19). DOI: 10.1063/1.4713939


State-of-the-art ab initio techniques have been applied to compute the potential energy curves for the electronic states in the A1Σu+, c3Πu, and a3Σu+ manifold of the strontium dimer, the spin-orbit and nonadiabatic coupling matrix elements between the states in the manifold, and the electric transition dipole moment from the ground X1Σg+ to the nonrelativistic and relativistic states in the A+c+a manifold. The potential energy curves and transition moments were obtained with the linear response (equation of motion) coupled cluster method limited to single, double, and linear triple excitations for the potentials and limited to single and double excitations for the transition moments. The spin-orbit and nonadiabatic coupling matrix elements were computed with the multireference configuration interaction method limited to single and double excitations. Our results for the nonrelativistic and relativistic (spin-orbit coupled) potentials deviate substantially from recent ab initio calculations. The potential energy curve for the spectroscopically active (1)0u+ state is in quantitative agreement with the empirical potential fitted to high-resolution Fourier transform spectra [A. Stein, H. Knöckel, and E. Tiemann, Eur. Phys. J. D 64, 227 (2011)]10.1140/epjd/e2011-20229-6. The computed ab initio points were fitted to physically sound analytical expressions, and used in converged coupled channel calculations of the rovibrational energy levels in the A+c+a manifold and line strengths for the A1Σu+←X1Σg+ transitions. Positions and lifetimes of quasi-bound Feshbach resonances lying above the 1S0 + 3P1 dissociation limit were also obtained. Our results reproduce (semi)quantitatively the experimental data observed thus far. Predictions for on-going and future experiments are also reported.

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