Solvent effects on the electronic structure and spectroscopic properties of a binuclear rhodium carbonyl complex: a DFT and TDDFT study.

contextThe binuclear rhodium(I) complex H

methodsAll calculations were performed with ORCA 6.1.1. Ground state geometry optimization used the r2SCAN-3c composite functional with a modified D4 dispersion correction and a small basis set correction term. Relativistic effects were treated via the zeroth-order regular approximation with DEF2-TZVPP basis sets; rhodium atoms employed the all-electron relativistic X2C-TZVPPall basis set. Exchange-correlation contributions used the chain-of-spheres resolution-of-identity (RIJCOSX) approximation. Solvent effects were incorporated using the SMD solvation model for ethanol, toluene, and chloroform. Excited state properties were computed using time-dependent DFT with the same functional/basis set combination. Excited state absorption, MCD (at 3000 G), fluorescence, and resonance Raman spectra were calculated using the ESD module. NBO analysis was performed with NBO6.0 following a single-point calculation (wb97xd/lanl2dz) on the optimized geometry. DOS and PDOS analyses were carried out; NCI and RDG analyses were performed with Multiwfn 3.8 and visualized with VMD 2.0.0a8.