4a,4b-Dihydrophenanthrene → cis-stilbene photoconversion: TD-DFT/DFT study.

Abstract

DHP → CS photoconversion was analyzed in terms of electron density redistribution for the first time. The following explanation for the non-recovery of the C4a-C4b bond upon CS relaxation is proposed: during this process, the Coulomb repulsion energy between these pairs of atoms increases by almost one and a half times, and their bonding by an electron at LUMO is insufficient to recover the C4a-C4b bond. According to calculations, upon CS relaxation, the linker connecting the benzene rings undergoes significant structural changes. In this case, the distance between the C4a and C4b atoms increases from 3.00Å to 3.28Å. Calculations showed that the C4a-C4b vibration of the DHP bond has a very low intensity. Therefore, thermal motion does not contribute to the rupture of this bond. All calculations were performed using the Gaussian16 software package at the B3LYP/6-311 + + G(d,p)/IEFPCM theory level. B3LYP was the only hybrid functional supported by Gaussian16, which ensured the cleavage of the C4a-C4b bond of DHP while optimizing its S1 excited state. A quantitative description of the redistribution of electron density in the studied conformers was carried out using the analysis of the NPA of atomic charges. Cyclohexane was used as an implicitly specified non-polar solvent. Visualization of molecular orbitals, and electron densities, as well as plotting of calculated IR spectra, were performed using the Gaussview6 software package.