Dimethyl fumarate molecule, crystal, and plane: Optical absorption measurement and structural/optoelectronic properties by density functional theory calculations

Dimethyl fumarate (DMF) is the main fumaric acid ester of the Fumaderm advanced medicament for the treatment of psoriasis and multiple sclerosis. Many properties of the DMF molecule and its crystal are still unknown. Here, the structural, electronic, and optical properties of DMF in molecular form and in the form of triclinic van der Waals crystals are addressed within the framework of density functional theory (DFT) formalism. The computations were performed using local density and generalized gradient exchange-correlation functionals, LDA and GGA, respectively, including one dispersion correction scheme for the former and two for the latter. Besides, the Δ-sol correction method was applied to improve the band-gap energy estimated from the DFT computations. The UV/Vis spectra of the DMF molecule solvated in ethanol and in the crystal were measured and compared with theoretical data obtained from time-dependent DFT (molecule) and DFT (crystal) calculations. One of the dispersion-corrected GGA functionals achieved very accurate descriptions of the lattice parameters, while analysis of the Kohn–Sham band structure indicated that the DMF crystal has a direct band-gap energy of 3.12 eV, differing from the experimental band-gap (4.00 eV) by 0.88 eV. By applying the Δ-sol correction method, the band-gap energy increased to 3.95 eV, only 0.05 eV below the experimental value. Lastly, simulations were also carried out for a single DMF monolayer, for which a band-gap of 3.26 eV was predicted. Hence, intermolecular interactions tend to decrease the electronic energy gap according to the sequence Gapcrystal < Gapmonolayer < Gapmolecule.