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High-levelab initiocalculations have been performed on the PBr radical by using multi-reference configuration interaction method plus Davidson correction (+Q) with correlation-consistent quadruple-ζ quality basis set. The potential energy curves (PECs) of the 22 Λ–S states of PBr have been obtained, most of which are reported for the first time. From the PECs of the bound states, the spectroscopic constants have been determined, in good agreement with the experimental results where available. Due to the large state density, there exhibits complicated interactions in the electronic excited states of PBr. The possible interactions by the spin–orbit coupling (SOC) effect have been discussed based on the evaluatedR-dependent spin–orbit matrix elements. The 51 Ω states, generating from the 22 Λ–S states after taking SOC into account, have been computed. The Λ–S component analysis of the wavefunctions for the Ω states indicates the strong interaction of the Λ–S states especially at the avoided crossing points and near the dissociation limits. Finally, the transition dipole moments of several transitions arising from upper Ω states to the X10+and X21 states and the corresponding radiative lifetimes have been studied. Our calculation results provide new information that should be valuable for further experimental studies on the electronic excited states of the PBr radical. [ABSTRACT FROM AUTHOR]