Unraveling the Impact of Flexibility and Solvent Effects on the UV-Vis Absorption Spectrum of Subphthalocyanine in Liquid Chloroform within the Born-Oppenheimer Molecular Dynamics Approach

A study based on Born-Oppenheimer molecular dynamics (BOMD) of the subphthalocyanine (SubPc) with a chloride attached to the central boron atom was carried out. The BOMD simulation is used to access the dynamic evolution of the SubPc in liquid chloroform, and the electronic absorption spectrum is calculated using the Time-Dependent Density Functional Theory (TDDFT) considering explicit solvent models. We show that the conformational changes and solvent effects produce a red shift of the Q-band, where the largest contribution is due to the geometry changes of the symmetric structure of SubPc. A large splitting (0.2 eV) of the first electronic transition is also described, and it originates as a shoulder in the Q-band, which according to previous experimental studies is attributed to a vibronic origin. The red shift is obtained in agreement with experiment within less than 0.1 eV. The splitting is a consequence of the symmetry breaking in the SubPc central ring structure occurring during the molecular dynamics, with a significant contribution to the large red shift and the broadening of the spectrum.