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

Journal of Chemical Physics - Tập 128 Số 2 - 2008
Yuzuru Kurosaki1, Leo Matsuoka1, Keiichi Yokoyama1, Atsushi Yokoyama2
1Kansai Photon Science Institute Quantum Beam Science Directorate, , Japan Atomic Energy Agency, Kizugawa, Kyoto 619-0215, Japan
2Tokai Research and Development Center Quantum Beam Science Directorate, , Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan

Tóm tắt

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 Λ-S states, XΣ+1, 2Σ+1, Σ+3, Π1, and Π3 are first calculated and then those for 13 Ω states are obtained by diagonalizing the matrix of the electronic Hamiltonian Ĥel plus the effective one-electron spin-orbit (SO) Hamiltonian ĤSO. Spectroscopic constants for the calculated ground X0+-state PEC with the Davidson correction are found to agree well with the experiment. Transition dipole moments (TDMs) between X0+ and the other Ω states are also obtained and the TDM between X0+ and A0+ is predicted to be the largest and that between X0+ and B0+ is the second largest around the equilibrium internuclear distance. The TDMs between X0+ and the Ω=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 X0+ PEC for the two isotopic analogs, Cs133I and Cs135I, are numerically obtained to investigate the isotope effect on the vibrational-level shift. It has been found that the maximized available isotope shift is ∼30cm−1 around v=136.

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Journal of Chemical Physics

Tập 128 Số 2

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