Direct High-Resolution Determination of the Singlet–Triplet Splitting in NH Using Stimulated Emission Pumping

A completely resolved spectrum of the strongly forbidden NH (a(1)Delta --X(3)Sigma(-)) transition is observed. The NH radicals in the excited a(1)Delta state are exclusively generated in a Nd:YAG laser photolysis of hydrazoic acid at a wavelength of 266 nm. The NH (a(1)Delta --X(3)Sigma(-)) intercombination transition around 794 nm is used to produce NH (X(3)Sigma(-)) applying the stimulated emission pumping technique. The ground state radicals are detected by laser-induced fluorescence (LIF). The energy splitting between the NH (X(3)Sigma(-), v = 0, J = 1, N = 0) state and the NH (a(1)Delta, v = 0, J = 2) state is determined with an accuracy of 0.1 cm(-1) to DeltaE = 12 687.8(65) cm(-1). In addition, the radiative lifetime tau of the NH (a(1)Delta --X(3)Sigma(-)) transition was estimated by a determination of the saturation intensity to be tau approximately 12.5 s. Copyright 1999 Academic Press.