Calculation of the Vibrationally Resolved, Circularly Polarized Luminescence of d‐Camphorquinone and (S,S)‐trans‐β‐Hydrindanone

Abstract

Circularly polarized luminescence (CPL), the differential emission of left- and right-handed circularly polarized light from a molecule, is modeled by using time-dependent density functional theory. Calculations of the CPL spectra for the first electronic excited states of d-camphorquinone and (S,S)-trans-beta-hydrindanone under the Franck-Condon approximation and using various functionals are presented, as well as calculations of absorption, emission, and circular dichroism spectra. The functionals B3LYP, BHLYP, and CAM-B3LYP are employed, along with the TZVP and aug-cc-pVDZ Gaussian-type basis sets. For the lowest-energy transitions, all functionals and basis sets perform comparably, with the long-range-corrected CAM-B3LYP better reproducing the excitation energy of camphorquinone but leading to a blue shift with respect to experiment for hydrindanone. The vibrationally resolved spectra of camphorquinone are very well reproduced in terms of peak location, widths, shapes, and intensities. The spectra of hydrindanone are well reproduced in terms of overall envelope shape and width, as well as the lack of prominent vibrational structure in the emission and CPL spectra. Overall the simulated spectra compare well with experiment, and reproduce the band shapes, emission red shifts, and presence or absence of visible vibrational fine structure.

Time‐Dependent Density Functional Theory for Calculating Origin‐Independent Optical Rotation and Rotatory Strength Tensors

“…Details of the approach used for the calculations and basis set benchmarks can be found in ref. [51], where we calculated FC factors from TDDFT to model absorption, emission, CD, and circular polarized luminescence (CPL) spectra of two organic molecules with carbonyl chromophores in the same way (see also the previous work by Lin et al [52] and Grimme and co-workers [53] ). In Figure 4 the calculated spectra are blue-shifted by a modest 1000 cm À1 (or 1/8 of an electron volt) to match the position of the most intense peak in the experimental spectrum.…”

Circularly Polarized Luminescence from Axially Chiral BODIPY DYEmers: An Experimental and Computational Study

“…In the present situation, it is also likely that the dependence of the magnetic and electric transition dipoles on the torsional motion cannot be disregarded. The full consideration of such an effect cannot be accomplished at a pure electronic level and it would require the inclusion of vibronic contributions beyond the Franck–Condon approximation …”

Conformational changes and chiroptical switching of enantiopure bis-helicenic terpyridine upon Zn2+ binding

“…Calculations at the LC-PBE0*/SV(P) level 14 with a continuum solvent model for CH 2 Cl 2 reproduce these modifications well and link them predominantly to the large conformational changes in the structure of the ligand 1 upon Zn(II) coordination. The simulated ECD spectrum of ligand 1 in the cis conformation of the terpy unit indeed clearly resembles the one calculated for 1· Zn(OAc) 2 (Figure 1).…”