Theoretical elucidation of the energy conversion rate in organic photovoltaic cells of the fullerene nanostructure derivatives. A density functional theory study

Abstract

A comparative theoretical study of the kinetics of the Diels–Alder (DA) reaction between empty fullerene (C[Formula: see text]) and lithium ion encapsulated fullerene ([Formula: see text]) with 1,3 cyclohexadiene (C[Formula: see text]H[Formula: see text]) was carried out. This reaction takes place in a photovoltaic cell. The effect of the encapsulated Li[Formula: see text] ion on the conversion rate of solar energy into electricity has been highlighted through calculations based on the density functional theory (DFT). In addition, a static study using the global conceptual DFT indices, as part of the demonstration of the significant electrophilic power of the fullerene nanostructure, was carried out to show the effect of encapsulating the Li[Formula: see text] ion in this nanoparticle on the electrophilic power of Li[Formula: see text]@C[Formula: see text] and therefore on the acceleration of the reaction. The relationship between the HOMOdonor–LUMOacceptor energy difference and the DA reaction acceleration, and therefore the acceleration of light conversion (a rapid conversion implies a small gap), has been thoroughly examined. Moreover, a mechanistic study of the kinetics of the DA reaction of the fullerene involved in an organic photovoltaic cell has been carried out. In this section, a concerted synchronous mechanism with no effect of Li[Formula: see text] encapsulation on the synchronicity of the reaction was observed. Finally, it was revealed that Li[Formula: see text]@C[Formula: see text] reacted approximately 2466 times faster than C[Formula: see text]. Moreover, the experimental results were found in good agreement with the computer calculations.

Diels–Alder cycloadditions of fullerene: Advances in mechanistic theory

“…25,26 Consequently, understanding the DA reaction mechanisms is crucial to the further development of fullerene science. 27,28 The Woodward-Hoffman rule and frontier orbital theory are often used to understand the cycloaddition reactions of fullerene. 24,29 Theoretical and experimental studies on the mechanism of DA cycloaddition to fullerene indicate a concerted pathway.…”

“…The DA reaction provides a reliable method to obtain six‐membered rings with good regio‐ and stereoselectivity, which is a powerful and popular tool for derivatizing fullerene 25,26 . Consequently, understanding the DA reaction mechanisms is crucial to the further development of fullerene science 27,28 …”