The sonoluminescence (SL) spectrum of Na atoms revealed that the Na line consists of two components, one of which is a broadened component (broad component) which is shifted from the original D lines, and the other is an unshifted narrow component (narrow component). We spatially separated the continuum, broad, and narrow components by capturing SL images using different optical filters. We also temporally separated these components by measuring SL pulses using respective band-pass filters. The SL image distribution and the timing of the SL pulses were different between the broad and narrow components. The results suggested that the broad and narrow components of Na emission are generated from different bubble populations. The dependences of SL spectra on ultrasonic frequency and dissolved rare gas (He, Ne, Ar, Kr, and Xe) were also investigated. It is concluded that the broad component and a blue satellite peak at 558 nm originate from van der Waals molecules composed of Na and rare-gas atoms. The narrow component was predicted to occur under temperature conditions at bubble collapse higher than that for the broad component.