The hydrogen-bonded complex of pyrazine and 1,1,1,3,3,3-hexafluoro-2-propanol (HFP) is strongly bound in the ground and first excited n pi* singlet states. Ground-state vapor-phase FTIR and supersonic-jet fluorescence excitation spectroscopy were utilized to obtain estimates of the binding energies in both states. The results, accurate to approximately 200 cm(-1), are 3400 cm(-1) in S-0 (40 +/- 2 kJ/mol) and 3000 cm(-1) in S-1 (n pi*, 35 +/- 2 kJ/mol). The 0(0)(0) and two excited vibrational bands of the complex, 6a(0)(1) at 583 and 10a(0)(2) at 790 cm(-1), were observed in the electronic spectrum. Pyrazine is a well-known example of an intermediate case molecule whose fluorescence decay curve when excited to SI displays a fast and a slow component. However, the complex in the vibrationless level of S-1 displays "statistical limit", or large-molecule radiationless decay, with no slow component in its fluorescence decay curve.