Revisiting the IR Spectra of HS in an Argon Matrix: Identification of (HS) ( ≤ 4) Clusters via the Spectral Assignment of Transitions.

Small-molecular clusters of HS up to tetramer have been experimentally identified in a cold and solid argon matrix by the spectral assignment of fundamental transitions for different HS:argon mixing ratios. Normal-mode frequency calculations at the MP2-CP/aug-cc-pV(Q + d)Z level have been used to support the spectral assignments. In addition, modulations in relative populations of different clusters due to the annealing of the deposited matrix and the preheating of the HS-argon gas mixture before deposition reinforced the spectral assignments. Variations in mixing ratio, annealing of the matrix, and preheating of the gas mixture have also been used, in a combined manner, to unambiguously identify the and bands of the HS monomer, which has been a matter of dispute for a long period. The two bands have been identified at 2634.4 and 2648.0 cm, respectively, while three bands at 2581.5, 2568.4, and 2547.6 cm have been assigned to H-bonded dimers, cyclic trimers, and cyclic tetramers, respectively. Multiple bands within 2550-2580 cm have been assigned to caged tetramers. The cooperative strengthening of S-H···S H bonds in cyclic HS clusters was evident from the linear increment in spectral shifts with cluster size.