Waveform design is a potentially significant approach to improve the performance of an imaging or detection system. Photoacoustic imaging is a rapidly developing field in recent years; however, photoacoustic waveform design has not been extensively investigated. This paper considers the problem of photoacoustic waveform design for parameter estimation under constraints on input energy. The use of information theory is exploited to formulate and solve this optimal waveform design problem. The approach yields the optimal waveform power spectral density. Direct inverse Fourier transform of the optimal waveform frequency spectrum amplitude is proposed to obtain a real waveform in the time domain. Absorbers are assumed to be stochastic absorber ensembles with uncertain duration and location parameters. Simulation results show the relationship between absorber parameter distribution and the characteristics of optimal waveforms. Comparison of optimal waveforms for estimation, optimal waveforms for detection (signal-to-noise ratio) and other commonly used waveforms are also discussed. The symmetry properties of the forward and inverse Fourier Transforms are used to analyze the time and frequency properties and provide a heuristic view of how different goals affect the choice of waveform.