This work presents a detailed analysis of enhanced Raman scattering of the pyridine-Ag-20 model system using time-dependent density functional theory. A consistent treatment of both the chemical and electromagnetic enhancements (EM) is achieved by employing a recently developed approach based on a short-time approximation for the Raman cross section. A strong dependence of the absolute and relative intensities on the binding site and excitation wavelength is found. The analysis of the Raman scattering cross sections shows the importance of different contributions to the enhancements, including static chemical enhancements (factor of 10), charge-transfer enhancements (10(3)), and EM enhancements (10(5)). The largest enhancement found (10(5)-10(6)) is due to the EM mechanism, with a small contribution from the chemical interaction. This suggests that the enhanced Raman scattering due to atomic clusters is comparable to findings on single nanoparticles. A combination of information about the vibrational motion and the local chemical environment provides a simple picture of why certain normal modes are enhanced more than others.