Transfer of Spectral Weight and Symmetry across the Metal-Insulator Transition in<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:msub><mml:mi>VO</mml:mi><mml:mn>2</mml:mn></mml:msub></mml:math>

We present a detailed study of the valence and conduction bands of VO2 across the metal-insulator transition using bulk-sensitive photoelectron and O K x-ray absorption spectroscopies. We observe a giant transfer of spectral weight with distinct features that require an explanation which goes beyond the Peierls transition model as well as the standard single-band Hubbard model. Analysis of the symmetry and energies of the bands reveals the decisive role of the V 3d orbital degrees of freedom. Comparison to recent realistic many body calculations shows that much of the k dependence of the self-energy correction can be cast within a dimer model.