The rateless multiple access (RMA) scheme is a promising distributed multiple access scheme to achieve simultaneous high reliability, low latency and massive connectivity. In this paper, we investigate the maximum likelihood (ML) decoding performance of the RMA scheme in an Additive white Gaussian noise (AWGN) channel with binary phase-shift keying (BPSK) modulation. For the first time, this paper derives the ensemble weight distribution of the RMA scheme. We derive an upper bound on the decoding error performance of the RMA scheme under ML decoding in an AWGN channel with BPSK modulation. Using the derived bound as the fitness function, we adopt the continuous genetic algorithm to optimize the parameters of the RMA scheme. Simulation results show the tightness of the derived bound and the superiority of the optimized degree distribution over the conventional degree distributions.