Ultrafast, asymmetric charge transfer and slow charge recombination in porphyrin/CNT composites demonstrated by time-domain atomistic simulation

Abstract

The versatile photochemical properties of porphyrin molecules make them excellent candidates for solar energy applications. Carbon nanotubes (CNTs) exhibit superior charge conductivity and have been combined with porphyrins to achieve efficient and ultrafast charge separation. Experiments show that the charge separated state lives less than 10 ps, which is too short for applications. Using real-time time-dependent tight binding density functional theory (DFTB) combined with non-adiabatic molecular dynamics (NAMD), we model photo-induced charge separation and recombination in two porphyrin/CNT composites. Having achieved excellent agreement with the experiment for the electron transfer from the porphyrins to the CNT, we demonstrate that hole transfer can be achieved upon CNT excitation, although in a less efficient way. By exciting the CNT one can extend light harvesting into lower energies of the solar spectrum and increase solar light conversion efficiency. We also show that the charge separated state can live over 1 ns. The two orders of magnitude difference from the experimental lifetime could arise due to the presence of defects or metallic tubes in the samples. The charge separated state is long-lived because the non-adiabatic electron–phonon coupling is very small, less than 1 meV, and the quantum coherence is short, 15–20 fs. The excited states in the isolated porphyrins and CNT live around 100 ps, in agreement with experiments as well. The porphyrin/CNT interaction occurs through the π-electron systems of the two species. The non-radiative relaxation is promoted by both high and low frequency phonons, with higher frequency phonons playing more important roles in electron relaxation than in hole relaxation. Low frequency phonons contribute significantly to the decay of the charge separated state, because they modulate the relative positions of the porphyrins and the CNT. The time-domain atomistic simulations provide a detailed understanding of the charge separation and recombination mechanisms, and generate valuable guidelines for the optimization of photovoltaic efficiency in modern nanoscale materials.