Spectroscopic properties of the low-lying 2B1, 2A1, 2A2, 4A2, 2B1(II), 4B1, 2B2(I), 2B2(II) electronic states of AsCl2 and AsBr2 have been studied with the complete active space self-consistent field (CASSCF) followed by multireference singles and doubles configuration interaction (MRSDCI) methods. In addition, the three low-lying electronic states of AsCl2+ and AsBr2+, (1A1,3B1,1B1) and the ground states of AsCl and AsBr were investigated. The bond dissociation energies of AsCl2, AsBr2, AsCl, and AsBr have been computed at the CASSCF/MRSDCI and CASSCF/second order configuration interaction (SOCI) levels as De(ClAs–Cl)=2.56 eV, De(BrAs–Br)=1.96 eV, De(As–Cl)=2.68 eV, and De(As–Br)=2.26 eV. The adiabatic ionization energies obtained in this work are 8.40 eV for AsCl2 and 8.33 eV for AsBr2. All these species have been found to possess bent geometries at their ground electronic states.

Spectroscopic properties and bending potential energy surfaces of 2B1, 2A1, 2A2, 2A2(2Πg), 4A2(4Πg), and 2B2 electronic states of SbCl2 and SbBr2, and three low-lying electronic states of SbCl2 + and SbBr2 +, (1A1, 3B1, 1B1), have been studied with complete active space self-consistent field (CASSCF) followed by multireference singles and doubles configuration interaction (MRSDCI) methods that included nearly 2 million configurations. The bond dissociation and adiabatic ionization energies of SbCl2, SbBr2, SbCl, and SbBr have been computed. The computed properties of these species are extensively compared with other group V dihalides.

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