Comprehensive analysis of DFT-3C methods with B3LYP and experimental data to model optoelectronic properties of tetracene

Abstract

Modern computational chemistry methods aid experimentalists in scrutinizing molecular systems for organic optoelectronic device fabrication. They are also helpful for device engineering, such as choosing metals for contact fabrication without sophisticated instrumentation. The B3LYP functional with 6-31G(d,p) or 6-311G(d,p) basis set is a widely used method in this regard. Recently, many upgraded methods, such as the three-fold corrected composite scheme (3C), have been reported to offer cost-effectiveness and better accuracy than the B3LYP. This is particularly interesting from a materials engineering point of view as these methods offer the possibility of rapidly screening the materials prior to the experimental analysis. In order to evaluate their suitability towards organic optoelectronic systems, in this work, we have used three composite schemes, namely B97-3C, PBEh-3C and HF-3C, along with B3LYP and the experimental data. The well-studied tetracene system is considered for the analysis, and different optoelectronic properties such as bandgap, reorganization energy, and absorption maximum are calculated theoretically and compared with the experimental data. The results indicate that though slightly expensive, B3LYP performs better than the 3C methods. Of the three, only PBEh-3C performs on par with B3LYP in accuracy and time. A note of caution is that these results should be inferred as this level of theory is adequate for the screening and modeling optoelectronic systems rather than a potential computational chemistry method.