The surface and interface of the metal nanoclusters and semiconducting nanomaterials play a key role in determining the electronic structure and overall photophysical properties. A single strand DNA stabilizes the metal nanoclusters, but it also influences the structural change, solvation free energy, and photophysical properties. On the other hand, surface and interface states in Pb and Cd chalcogenide nanomaterials affect the phonon mediated hot carrier relaxation. We applied DFT and DFT based non-adiabatic dynamics methods to study the surface and interface’s effects on the photoexcited processes. In the first part, we have studied the Ag nanoclusters' photophysical properties that are affected by the structural isomers, redox potential, nucleobase passivation, and cluster size. Ag nanoclusters are shown alternative reduction potential, which makes nanoclusters of singlet spin multiplicity thermodynamically favorable. Besides, the optically bright transition in the range of 2.5-3.5 eV is shown metal to ligand charge transfer. It is modulated by the s+p+d orbital mixing in the hole and electron states. We also simulate the charge transfer from the photoexcited PbS QD to organic dye (PDI) attached to the QD surface. Depending on the linker group and the dipole moment of neighboring passivating ligands, the PDI-QD conformations are varies. In response to structural change, the total dipole moment is modulated, changing its electronic structure and hence the photoexcited electron transfer rate from the PbS QD to PDI. We also investigate the inorganic-inorganic interactions in the PbCl2 bridged PbSe NPL and PbSe|CdSe Janus heterostructure. The energy dissipation rate of hot electrons is slower in NPL than the hot hole, while hot e-h relaxed to the band-edge by ≈1.0ps in the QD. The slower relaxation rate is rationalized by a large average intraband energy difference and smaller coupling term. Besides, the hot carriers in the NPL are spatially separated by ≈1.00 ps, which is a favorable condition for the carrier multiplication process. In Janus QD, (100) interfacial layer creates a structural mismatch in the CdSe part. Besides, the energy offset between the valance localized on PbSe and CdSe part is minimum in the PbSe Janus QD of an interface of (111) facet.