Validations of CNDOL approximate Hamiltonian as a fast and reliable method to obtain vertical excitation energies in polyatomic systems

Theoretical prediction of vertical excitation energies and an estimation of charge distributions of polyatomic systems can be calculated, through the configuration interaction of single (CIS) excited determinants procedure, with the CNDOL (Complete Neglect of Differential Overlap considering the l azimuthal quantum number) Hamiltonians. This method does not use adjusted parameters to fit experimental data and only employ a priori data on atomic orbitals and simple formulas to substitute large computations of electronic integrals. In this sense, different functions for bi-electron integrals have been evaluated in order to improve the approximate Hamiltonian. The reliability of predictions and theoretical consistence has been tested with a benchmark set of organic molecules that covers important classes of chromophores including polyenes and other unsaturated aliphatic compounds, aromatic, hydrocarbons, heterocycles, carbonyl compounds, and nucleobases. The calculations are done at identical geometries (MP2) with the same basis set (6-31G) for these medium-sized molecules and the obtained results were statistically compared with other analogous methods and experimental data. The accuracy of prediction of each CNDOL vertical transitions energy increases while the active space is more complete allowing the best variational optimization of CIS matrices i.e. molecular excited states. Moreover and due to the feasible computation procedure for large polyatomic systems, the studies have been extended, as a preliminary work, in the field of optoelectronic materials for photovoltaic applications. Hence, the excitation energies of different conjugated Phenyl-cored Thiophene Dendrimers optimized by DFT (Density Functional Theory) were calculated and show good agreement with the experiment data. The predicted charge distribution during the excitation contributes to understand the photophysics process on these kind materials. (Full text)