Deciphering the dual emission in the photoluminescence of Au14Cd(SR)12: A theoretical study using TDDFT and TDDFT + TB.

Determining excited state processes for small nanoclusters, specifically gold, aids in our ability to fine-tune luminescent materials and optical devices. Using TDDFT and TDDFT + TB, we present a detailed theoretical explanation for the dual emission peaks displayed in Au14Cd(S-Adm)12 (Adm = adamantane). As dual emission is relatively rare, we decipher whether the mechanism originates from two different excited states or from two different minima on the same excited state surface. This unique mechanism, which proposes that the dual emission results from two minima on the first excited state, stems from geometrical changes in the bi-tetrahedron core during the emission process.