Multiconfigurational Calculations and Experimental Resonant Raman/SERRS of a Donor-Acceptor Thiadiazole Dye.

The resonant Raman (RR) and resonant SERS spectra of the thiadiazole-based dye dibromobenzo[]-1,2,5-thiadiazole (DBTD) were studied through multiconfigurational XMS-CASPT2/CASSCF and experimental methods in solution. The results indicate that the S excited state of DBTD is described by π → π* with internal CT from the benzene ring to the thiadizole. In resonance conditions at 364 nm, the RR spectrum shows intensifications in modes that describe extensive geometrical changes at both the benzene ring and the thiadiazole region, indicating an internal CT character to the S.

Marrying SPR excitation and metal-support interactions: unravelling the contribution of active surface species in plasmonic catalysis.

Plasmonic catalysis takes advantage of the surface plasmon resonance (SPR) excitation to drive or accelerate chemical transformations. In addition to the plasmonic component, the control over metal-support interactions in these catalysts is expected to strongly influence the performances. For example, CeO2 has been widely employed towards oxidation reactions due to its oxygen mobility and storage properties, which allow for the formation of Ce3+ sites and adsorbed oxygen species from metal-support interactions.