Density functional theory (DFT) has been used to investigate the conformations and thermochemistry on the singlet and triplet potential energy surfaces (PES) of Cr2(CO)10. The global minimum energy structure for the lowest singlet state of C2h symmetry is consistent with a model of two interacting Cr(CO)5 fragments in which one carbonyl in each fragment acts as an asymmetric four-electron donor bridging carbonyl, with chromium-chromium distances of 2.93 Å (B3LYP) or 2.83 Å (BP86). Avoiding a Cr⋯Cr bond by incorporating four-electron donor CO groups in this way allows each chromium atom in singlet Cr2(CO)10 to attain the favored 18-electron configuration by using, in a simple picture of the bonding, only the six octahedral sp3d2 hybrids. The dissociation energy to two Cr(CO)5 fragments or to Cr(CO)6 + Cr(CO)4 fragments is predicted to be 10 kcal mol−1. The lowest triplet state of Cr2(CO)10 is predicted to lie ∼10 kcal mol−1 above the singlet global minimum. In the case of triplet Cr2(CO)10 the lowest energy minima were found to be of C2 and C2h symmetry, with similar energies. The chromium-chromium distances in triplet Cr2(CO)10 were found to be shorter than those in the corresponding singlet structures, namely 2.81 (B3LYP) or 2.68 Å (BP86) suggesting a σ + 2(1/2) π Cr[double bond, length as m-dash]Cr double bond similar to the O[double bond, length as m-dash]O bond in O2 or the Fe[double bond, length as m-dash]Fe bond in the experimentally observed triplet state (Me5C5)2Fe2(μ-CO)3.