The laser resonance absorption technique has been used to determine the relaxation rate of electronically excited neodymium vapor during its expansion into vacuum. Significant increases of population into ground and 1128‐cm−1levels were found. Analysis shows that interaction between excited metastable atoms and electrons are much more important for relaxation than atom‐atom collisions. The final population of neodymium appears to be frozen at a temperature lower than the surface temperature of melt.