Assessment of long-range corrected density functional theory on the absorption and vibrationally resolved fluorescence spectrum of carbon nanobelts.

Abstract

Time-dependent (TD) density functional theory (DFT) and Franck-Condon Hertzberg-Teller (FCHT) calculations of various DFT functionals [B3LYP, CAM-B3LYP, ωB97XD, and optimally tuned (OT) long-range corrected (LC)-BLYP] were performed to examine how well DFT functionals can predict the experimental absorption and fluorescence spectra of a 12-carbon nanobelt (CNB). OT-LC-BLYP reproduced the experimental absorption spectrum well in terms of the peak position and intensity in the case of using a basis set with a diffuse function, such as 6-31+G(d,p) and 6-311+G(d,p), whereas B3LYP showed a red-shift in the peak positions and CAM-B3LYP and ωB97XD, which have a long-range HF exchange, showed blue shifts. Regarding the fluorescence spectrum calculations with FCHT using 6-311+G(d,p), the OT-LC-BLYP reproduced both the peak intensities and positions closest to the experimental spectrum. B3LYP, however, showed red-shifted peaks, and ωB97XD showed blue-shifted peaks. CAM-B3LYP provided less blue-shifted peaks, but the relative peak intensities mismatched the experimental ones. Furthermore, calculations of the absorption and vibrationally resolved fluorescence spectra of 16-CNB and 24-CNB using OT-LC-BLYP/6-311+G(d,p) showed absorption and fluorescence spectra close to the experimental spectra with high accuracy. Moreover, the application of a polarizable continuum model (dichloromethane) produced a red shift in the peak positions of the absorption spectrum with increasing intensity but an increase in the peak intensities of the fluorescence calculations without shifting the peak position.