Based on an atomically detailed surface growth model, we have performed kinetic Monte Carlo (KMC) simulations to determine the surface chemical composition of plasma deposited hydrogenated amorphous silicon (a-Si:H) thin films as a function of substrate temperature. Our surface growth kinetic model consists of a combination of various surface rate processes, including silyl (SiH3) radical chemisorption onto surface dangling bonds or insertion into Si–Si surface bonds, SiH3 physisorption, SiH3 surface diffusion, abstraction of surface H by SiH3 radicals, surface hydride dissociation reactions, as well as desorption of SiH3, SiH4, and Si2H6 species into the gas phase. Transition rates for the adsorption, surface reaction and diffusion, and desorption processes accounted for in the KMC simulations are based on first-principles density-functional-theory computations of the corresponding optimal pathways on the H-terminated Si(001)-(2×1) surface. Results are reported for two types of KMC simulations. The first employs a fully ab initio database of activation energy barriers for the surface rate processes involved and is appropriate for modeling the early stages of growth. The second uses approximate rates for all the relevant processes to account properly for the effects on the activation energetics of interactions between species adsorbed at neighboring surface sites and is appropriate to model later stages of growth toward a steady state of the surface composition. The KMC predictions for the temperature dependence of the surface concentration of SiHx(s) (x = 1,2,3) species, the surface hydrogen content, and the surface dangling-bond coverage are compared to experimental measurements on a-Si:H films deposited under operating conditions for which the SiH3 radical is the dominant deposition precursor. The predictions of both KMC simulation types are consistent with the reported experimental data, which are based on in situ attenuated total reflection Fourier transformed infrared spectroscopy.