This paper is a continuation of previous studies (de la Cal et al 2007 J. Nucl. Mater. 363-365 764, de la Cal et al 2007 Proc. 34th EPS Conf. (Poland, Warsaw) P 2.029), where hydrogen recycling under ionizing plasma conditions was analysed by spatially resolved H(alpha)-emission spectroscopy with a tangentially viewing camera looking at a poloidal limiter of the TJ-II stellarator operated with a low density, high temperature plasma edge (n(e) = (1-10) x 10(12) cm(-3) and T(e) = 40-400eV). In this study, the first objective is to validate for hydrogen the recently implemented EIRENE code(a) by comparing simulated H(alpha)-emission chords with that obtained experimentally. The second objective is to analyse the atom and molecular neutral distributions in front of the limiter and at other plasma and chamber locations. The third one is to study the atomic and molecular reactions involved in the dissociation, ionization and excitation reactions, as calculated from the EIRENE code, in order to study hydrogen atomic and molecular physics in a low density, high temperature fusion plasma edge, with special focus on interpretation of H(alpha)-emission. The contribution of the different reactions to the emission is analysed as a function of plasma radius. A relevant result obtained from EIRENE under this item is that the main precursor of the molecular H(alpha)-emission is not H(2) as proposed in many previous studies, but H(2)(+).