Empirical potential energy surface for Ar·SH/D and Kr·SH/D

Experimental data from vibrationally and rotationally resolved laser induced fluorescence experiments have been used to produce potential energy surfaces (PES) for the excited à 2Σ+ states of the Ar·SH and Kr·SH van der Waals complexes. This was done using a potential energy functional form first suggested by Bowman and co-workers1 for Ar·OH/D. A discrete variable representation (DVR) of the vibration–rotation Hamiltonian was used in combination with the Implicitly Restarted Lanczos Method and Sequential Diagonalization Truncation (SDT) of the DVR Hamiltonian. This approach takes advantage of the sparseness of the DVR Hamiltonian and the reduced order of the SDT representation. This combination of methods greatly reduces the amount of computational time needed to determine the eigenvalues of interest. This is important for the determination of the PES that results from minimizing the difference between the experimental and theoretically predicted values for the vibronic energy levels and their corresponding rotational constants. In addition this procedure was helpful in assigning the absolute vibrational quantum numbers for the deuterated species for which less experimental data was available. Plots of the calculated wavefunctions cor-