The ultrafast radiationless decay mechanism of photoexcited cytosine has been theoretically supported by exploring the important potential energy surfaces using multireference configuration-interaction ab initio methods for the gas-phase keto-tautomer free base. At vertical excitation, the bright state is S-1 (pi pi*) at 5.14 eV, with S-2 (n(N)pi*) and S-3 (n(O)pi*) being dark states at 5.29 and 5.93 eV, respectively. Minimum energy paths connect the Franck-Condon region to a shallow minimum on the pi pi* surface at 4.31 eV. Two different energetically accessible conical intersections with the ground state surface are shown to be connected to this minimum. One pathway involves N-3 distorting out of plane in a sofa conformation, and the other pathway involves a dihedral twist about the C-5-C-6 bond. Each of these pathways from the minimum contains a low barrier of 0.14 eV, easily accessed by low vibronic levels. The path involving the N-3 sofa distortion leads to a conical intersection with the ground state at 4.27 eV. The other pathway leads to an intersection with the ground state at 3.98 eV, lower than the minimum by about 0.3 eV. Comparisons with our previously reported study of the fluorescent cytosine analogue 5-methyl-2-pyrimidinone (5M2P) reveal remarkably similar conformational distortions throughout the decay pathways of both bases. The different photophysical behavior between the two molecules is attributed to energetic differences. Vertical excitation in cytosine occurs at a much higher energy initially, creating more vibrational energy than 5M2P in the Franck-Condon region, and the minimum S-1 energy for 5M2P is too low to access an intersection with the ground state, causing population trapping and fluorescence. Calculations of vertical excitation energies of 5-amino-2-pyrimidinone and 2-pyrimidinone reveal that the higher excitation energy of cytosine is likely due to the presence of the amino group at the 4-position.