Rovibrational dynamics of the strontium molecule in the Asideset{^1}{u+}{Σ}, c3Πu, and asideset{^3}{u+}{Σ} manifold from state-of-the-art ab initio calculations
Abstract
State-of-the-art ab initio techniques have been applied to compute the potential energy curves for the electronic states in the Asideset{^1}{u+}{Σ}, c3Πu, and asideset{^3}{u+}{Σ} 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 Xsideset{^1}{g+}{Σ} 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)0_u^+ 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 Asideset{^1}{u+}{Σ}leftarrow Xsideset{^1}{g+}{Σ} 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.
- Publication:
-
Journal of Chemical Physics
- Pub Date:
- May 2012
- DOI:
- 10.1063/1.4713939
- arXiv:
- arXiv:1203.4524
- Bibcode:
- 2012JChPh.136s4306S
- Keywords:
-
- ab initio calculations;
- configuration interactions;
- coupled cluster calculations;
- dissociation;
- electric moments;
- Fourier transform spectra;
- ground states;
- molecular moments;
- potential energy surfaces;
- resonant states;
- rotational-vibrational states;
- spin-orbit interactions;
- strontium;
- transition moments;
- 33.15.Mt;
- 33.20.Vq;
- 33.20.Wr;
- 31.15.aj;
- 31.15.am;
- 33.15.Kr;
- Rotation vibration and vibration-rotation constants;
- Vibration-rotation analysis;
- Vibronic rovibronic and rotation-electron-spin interactions;
- Relativistic corrections spin-orbit effects fine structure;
- hyperfine structure;
- Relativistic configuration interaction and many-body perturbation calculations;
- Electric and magnetic moments polarizability and magnetic susceptibility;
- Physics - Chemical Physics
- E-Print:
- Final version, accepted for publication in Journal of Chemical Physics