We have benchmarked photon beam simulations with the EGS4 user code BEAM [Rogers et al., Med. Phys. 22, 503-524 (1995)] by comparing calculated and measured relative ionization distributions in water from the 10 and 20 MV photon beams of the NRC linac. Unlike previous calculations, the incident electron energy is known independently to 1%, the entire extra-focal radiation is simulated, and electron contamination is accounted for. The full Monte Carlo simulation of the linac includes the electron exit window, target, flattening filter, monitor chambers, collimators, as well as the PMMA walls of the water phantom. Dose distributions are calculated using a modified version of the EGS4 user code DOSXYZ which additionally allows scoring of average energy and energy fluence in the phantom. Dose is converted to ionization by accounting for the (L/rho)water(air) variation in the phantom, calculated in an identical geometry for the realistic beams using a new EGS4 user code, SPRXYZ. The variation of (L/rho)water(air) with depth is a 1.25% correction at 10 MV and a 2% correction at 20 MV. At both energies, the calculated and the measured values of ionization on the central axis in the buildup region agree within 1% of maximum ionization relative to the ionization at 10 cm depth. The agreement is well within statistics elsewhere. The electron contamination contributes 0.35(+/- 0.02) to 1.37(+/- 0.03)% of the maximum dose in the buildup region at 10 MV and 0.26(+/- 0.03) to 3.14(+/- 0.07)% of the maximum dose at 20 MV. The penumbrae at 3 depths in each beam (in g/cm2), 1.99 (dmax, 10 MV only), 3.29 (dmax, 20 MV only), 9.79 and 19.79, agree with ionization chamber measurements to better than 1 mm. Possible causes for the discrepancy between calculations and measurements are analyzed and discussed in detail.