Exact random walk definition of the collisional-radiative ionization and recombination coefficients

The collisional-radiative ionization and recombination coefficients are shown to be expressible in terms of the 'total probability', from initial level i to final level j, which excludes intermediate returns to the initial level. Applications are made to three-level and four-level systems to illustrate the method of calculation and compare with an approximation currently used.