CrF2 was studied by combined application of quantum-chemical calculations and gas-phase electron diffraction. Coupled cluster and density functional computations found the ground electronic state to be a quasi-linear B-5(2) state, which at linearity correlates with a (5)A(2) state to become a Renner-Teller (5)Pi(g) state. Several low-lying electronic states and the shallow bending potentials of the molecule combined with high-temperature experimental conditions make the single-molecule/single-state approach for the electron diffraction analysis unacceptable for this system. Instead, a multi-state approach was needed to determine the vapor composition and the structure, with the vapor consisting of three electronic states (82% B-5(2)/(5)Pi(g), 12% (5)A(2)/(5)Pi(g), 6% (5)Sigma(+)(g)). (C) 2008 Elsevier B. V. All rights reserved.