Computational Insights Into Betanin for Dsscs: Unraveling Deprotonation Variations and Identifying Optimal Anchoring Sites on TiO2

Abstract Betanin (Bn), a natural dye in the Betalains family, predominantly takes on a cationic form known as Bn + . However, it exists in a neutral state as Bn_C2, Bn_C15, and Bn_C17 by losing an H + from one of its carboxylic acids. Density functional theory (DFT) and Time‐dependent density functional theory (TD‐DFT) studies evaluate the efficiency of each betanin form and pinpoint the most probable anchoring point to TiO 2 . The Bn_C17 variant stands out as a highly promising candidate for DSSC cells, demonstrating a distinctive combination of electron injection efficiency, electrochemical performance, hole transport capabilities, and photovoltaic behavior. Considering factors like adsorption energy, binding mode, structural compatibility, electronic properties, and absorption characteristics, Bn_C17@TiO 2 emerges as the most favorable dye@TiO 2 complex among the studied betanin forms for DSSC applications. Contrastingly, the C2‐COOH anchoring point presents challenges with monodentate binding, a different orientation, and potential load distribution issues. This behavior, resembling that of a p‐type dye, differs from the n‐type behavior exhibited by the C15‐COOH and C17‐COOH forms, making the latter two more suitable as sensitizers. Consequently, C2‐COOH may not be the optimal anchoring point for TiO 2 in the investigated betanin forms, especially when compared to the more favorable C17‐COOH anchoring point.