1. Ab initio molecular-orbital study of the trichlorine radical, Cl3
- Author
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Qiang Cui, Michael C. Heaven, Keiji Morokuma, J. E. Stevens, W. G. Lawrence, and Alexey L. Kaledin
- Subjects
Chemistry ,Ab initio ,General Physics and Astronomy ,Configuration interaction ,Bond length ,symbols.namesake ,Ab initio quantum chemistry methods ,Excited state ,symbols ,Molecular orbital ,Physical and Theoretical Chemistry ,Atomic physics ,van der Waals force ,Ground state - Abstract
We report a rigorous ab initio study of the ground and low-lying excited-state potential-energy surfaces (PESs) of the Cl3 radical at CASSCF, CASPT2, and MRSDCI levels of theory. The ground state has two Cl⋯Cl2 van der Waals complexes, XL and X′B. The linear asymmetric minimum (XL) is 2Π, with a Cl–Cl distance r=3.90 bohr, and a Cl–M (M: the Cl2 center-of-mass) distance R=8.70 bohr. The bent asymmetric minimum (X′B) is of 2A′ symmetry, with r=3.90 bohr, R=6.85 bohr, and the angle between r and R, γ=68.4°. Spin–orbit CI (configuration interaction) predicts that the global minimum is linear XL (2Π3/2) with a bond dissociation energy of De(Cl2(X)-Cl) of 280 cm−1. Low-lying doublet excited states have only one strongly bound structure, a linear symmetric AL (1 2Πg) state with a bond distance of 4.67 bohr. This state is bound by ∼4300 cm−1 with respect to the Cl2(3Πu)+Cl asymptote, and its minimum lies about 8700 cm−1 above the XL van der Waals minimum. Transition dipole moment calculations show that t...
- Published
- 1998