Systematic First-Principles Configuration-Interaction Calculations of Linear Optical Absorption Spectra in Silicon...

We have performed first-principles electron-correlated calculations employing large basis sets to optimize the geometries and to compute linear optical absorption spectra of various low-lying conformers of silicon hydrides: Si₂H₂, n = 1, 2, 3. The geometry optimization for various isomers was carried out at the coupled-cluster singles-doubles-perturbative-triples [CCSD(T)] level of theory, while their excited states and absorption spectra were computed using a large-scale multireference singles-doubles configuration-interaction approach, which includes electron-correlation effects at a sophisticated level. Our calculated spectra are the first ones for Si₂H₂ and Si₂H₄ conformers, while for Si₂H₆, we obtain excellent agreement with the experimental measurements, suggesting that our computational approach is reliable. Our calculated absorption spectra exhibit a strong structure-property relationship, suggesting the possibility of identifying various conformers based on their optical absorption fingerprints. Furthermore, we have also performed geometry optimization for the selected optically excited states, providing insights into their character.