Quantum Chemical and Trajectory Surface Hopping Molecular Dynamics Study of Iodine‐Based BODIPY Photosensitizer

ABSTRACT

A computational study of I‐BODIPY (2‐ethyl‐4,4‐difluoro‐6,7‐diiodo‐1,3‐dimethyl‐4‐bora‐3a,4a‐diaza‐s‐indacene) has been carried out to investigate its key photophysical properties as a potential triplet photosensitizer capable of generating singlet oxygen. Multireference CASPT2 and CASSCF methods have been used to calculate vertical excitation energies and spin–orbit couplings (SOCs), respectively, in a model (mono‐iodinated BODIPY) molecule to assess the applicability of the single‐reference second‐order algebraic diagrammatic construction, ADC(2), method to this and similar molecules. Subsequently, time‐dependent density functional theory (TD‐DFT), possibly within the Tamm–Dancoff approximation (TDA), using several exchange‐correlation functionals has been tested on I‐BODIPY against ADC(2), both employing a basis set with a two‐component pseudopotential on the iodine atoms. Finally, the magnitudes of SOC between excited electronic states of all types found have thoroughly been discussed using the Slater–Condon rules applied to an arbitrary one‐electron one‐center effective spin–orbit Hamiltonian. The geometry dependence of SOCs between the lowest‐lying states has also been addressed. Based on these investigations, the TD‐DFT/B3LYP and TD‐DFT(TDA)/BHLYP approaches have been selected as the methods of choice for the subsequent nuclear ensemble approach absorption spectra simulations and mixed quantum‐classical trajectory surface hopping (TSH) molecular dynamics (MD) simulations, respectively. Two bright states in the visible spectrum of I‐BODIPY have been found, exhibiting a redshift of the main peak with respect to unsubstituted BODIPY caused by the iodine substituents. Excited‐state MD simulations including both non‐adiabatic effects and SOCs have been performed to investigate the relaxation processes in I‐BODIPY after its photoexcitation to the state. The TSH MD simulations revealed that intersystem crossings occur on a time scale comparable to internal conversions and that after an initial phase of triplet population growth a “saturation” is reached where the ratio of the net triplet to singlet populations is about 4:1. The calculated triplet quantum yield of 0.85 is in qualitative agreement with the previously reported experimental singlet oxygen generation yield of 0.99 0.06.