Theoretical study of cis-trans isomer of 2-hydroxy-5-methyl-2'-nitroazobenzene: DFT insight

Abstract

Context: The synthesis of azobenzene materials is an important aspect of the research in the field of photo-switch materials. It is currently thought that azobenzene molecules exist in the cis and trans form of molecular structure configuration. However, the reaction process allowing for reversible energy switches from trans to cis form is still challenging. Therefore, it is crucial to understand the molecular properties of the azobenzene compounds in order to provide reference for future synthesis and application. Affirmation supporting this perspective has been substantially derived from theoretical results in the isomerization process and whether these molecular structures may affect the electronic properties entirely needs to be confirmed. In this study, I give my effort to understand the molecular structure properties of the cis and trans form of azobenzene molecule from 2-hydroxy-5-methyl-2'-nitroazobenzene (HMNA). Their chemistry phenomena are investigated using the density functional theory (DFT) method. This study shows that the trans-HMNA has a molecular size of 9.0 Å and the cis-HMNA has a molecular size of 6.6 Å. The trans-HMNA exhibits an electronic transition of π → π* type driven by an azo bond, whereas the cis-HMNA exhibits an electronic transition of n → π* type with respect to the non-bonding electrons of oxygen and nitrogen atoms. Therefore, the HMNA mechanism pathway from trans to cis form is feasible to undergo at the inversion pathway in the ground state.

Methods: All DFT calculations were performed using the Gaussian Software Packages (Gaussian 09 Revision-A.02 and GaussView 5.0.8). Gaussum 3.0 software was selected to visualize the molecular orbital levels in the density of states diagram. The optimized molecular geometrical parameter was calculated using B3LYP/cc-pVTZ level in the gas phase. TD-DFT with M06-2X/cc-pVTZ level was used as a method for the precise interpretation of excited states in molecular systems.

Keywords: Azobenzene; DFT; Isomer; Structure.