The phosphorescence excitation spectrum of isolated 4-H-1-benzopyrane-4-thione molecules (BPT) in a pulsed supersonic jet was investigated by direct excitation of the first excited triplet state, S-0 --> T-1. The electronic origin at 15828 cm(-1) is assigned to the transition S-0,S-0 --> T-1z,T-0, the transition S-0,S-0 reversible arrow T-1(xy,0) is too weak to be detected with this method. The triplet lifetime tau(T1z,0) approximate to 11 mu s is compatible with extrapolated values for BPT in dilute solutions. Vibronic transitions S-0,S-0 --> T-1z,T-v were measured up to similar to 1940 cm(-1) above the origin; the vibrational structure of TI was compared with the vibrational structure of S-2. S-0,S-0 --> S-1,S-v absorptions were not observed in the laser-induced phosphorescence experiment. Hot bands were observed under specific experimental conditions. (C) 1997 Elsevier Science B.V.The phosphorescence excitation spectrum of isolated 4-H-1-benzopyrane-4-thione molecules (BPT) in a pulsed supersonic jet was investigated by direct excitation of the first excited triplet state, S-0 --> T-1. The electronic origin at 15828 cm(-1) is assigned to the transition S-0,S-0 --> T-1z,T-0, the transition S-0,S-0 reversible arrow T-1(xy,0) is too weak to be detected with this method. The triplet lifetime tau(T1z,0) approximate to 11 mu s is compatible with extrapolated values for BPT in dilute solutions. Vibronic transitions S-0,S-0 --> T-1z,T-v were measured up to similar to 1940 cm(-1) above the origin; the vibrational structure of TI was compared with the vibrational structure of S-2. S-0,S-0 --> S-1,S-v absorptions were not observed in the laser-induced phosphorescence experiment. Hot bands were observed under specific experimental conditions. (C) 1997 Elsevier Science B.V.