Ab initio study on the ground and low-lying excited states of cesium iodide (CsI).

Potential energy curves (PECs) for the ground and low-lying excited states of the cesium iodide (CsI) molecule have been calculated using the internally contracted multireference configuration interaction calculation with single and double excitation method with the relativistic pseudopotentials. PECs for seven Lambda-S states, X 1Sigma+, 2 1Sigma+, 3Sigma+, 1Pi, and 3Pi are first calculated and then those for 13 Omega states are obtained by diagonalizing the matrix of the electronic Hamiltonian H(el) plus the effective one-electron spin-orbit (SO) Hamiltonian H(SO). Spectroscopic constants for the calculated ground X 0+-state PEC with the Davidson correction are found to agree well with the experiment. Transition dipole moments (TDMs) between X 0 and the other Omega states are also obtained and the TDM between X 0+ and A 0+ is predicted to be the largest and that between X 0+ and B 0+ is the second largest around the equilibrium internuclear distance. The TDMs between X 0+ and the Omega=1 states are estimated to be nonzero, but they are notably small as compared with those between the 0+ states. Finally, vibrational levels of the X 0+ PEC for the two isotopic analogs, (133)CsI and (135)CsI, are numerically obtained to investigate the isotope effect on the vibrational-level shift. It has been found that the maximized available isotope shift is approximately 30 cm(-1) around nu=136.

Photoexcitation of K-shell and L-shell hollow beryllium.

We have observed K-shell and L-shell hollow beryllium atoms (2s(2)2p3s and 1s3s(2)3p) created by photoexcitation using synchrotron radiation. Resonance shapes were fitted to the Fano profile and the parameters were deduced. A Dirac-Fock calculation was performed to identify the configuration of the peaks and to predict other hollow atomic peaks. The results of the calculation were in good agreement with the experimental data. The comparison of the transition strength has revealed that the three-electron photoexcitation to the 1s3s(2)3p configuration is stronger than the two-electron photoexcitation to the 2s(2)2p3s configuration. This is attributed to the large overlap between the 2s orbital of the ground state (1s(2)2s(2)) with the orbital of the L-shell hollow state (1s3s(2)3p).