Abstract The kinetics of two-step photoionization of barium atoms through excited P 1 1 , 3 levels was studied by numerical simulation method in the optically dense approximation. The first laser at wavelength λ 1 = 553.5 nm ( λ 1 = 791 nm) pumps transition S 0 1 ↔ P 1 1 ( S 0 1 ↔ P 1 3 ). The second laser with λ 2 = 266 nm ( λ 2 = 310 nm) ionizes atoms from the level P 1 1 ( P 1 3 ). The third probe laser with wavelength λ i = 493.41 nm causes resonant fluorescence of barium ions. It is shown that the metastable D 2 3 from the D 1 , 2 , 3 3 triplet in barium is strongly populated through P 1 <