Abstract
AbstractVertical, well-to-well, and adiabatic ionization energies (IEs) and electron affinities (EAs) were calculated for the n=1-10 [n]acenes using a wide range of semiempirical, Hartree-Fock, density functional, and second order Moller-Plesset perturbation theory model chemistries. None of the model chemistries examined were able to accurately predict the IEs or EAs for both short- through mid-length [n]acenes, as well as for extrapolations to the polymeric limit, when compared to available experimental and benchmark theoretical data. Provided a minimal basis set size is employed, basis set effects on predicted IEs and EAs are not significant relative to the choice of model chemistry. The poor IE/EA prediction performance for the parent [n]acenes likely extends to their substituted derivatives and heteroatom substituted analogs. Consequently, caution should be exercised in the application of non-high level calculations for estimating the IE/EA of these important classes of materials.
Highlights
31 The [n]acenes and their derivatives offer potential in the field of organic electronics [1,2,3]
B3LYP/6-31G(d) calculations on the decacene cation failed to converge; this compound was omitted from well-to-well ionization energy (WWIE) and adiabatic ionization energy (AIE) calculations
well-to-well ionization energy 99 (WWIE)/AIE and well-to-well electron affinity (WWEA)/adiabatic electron affinity 96 (AEA) calculations for the n=8-9 [n]acene cations and n=7-10 [n]acene anions, respectively, make use of optimized B3LYP/6-31G(d) geometries for which corresponding frequency calculations were not conducted, and employ estimated zero-point energy and thermal corrections extrapolated from lower homologs. 108 Using the B3LYP/6-31G(d) optimized geometries for the neutral form of each compound, vertical ionization energies (VIEs) were calculated for the n=1-10 [n]acenes across a broad range of model chemistries at the x/TZVP//B3LYP/6-31G(d) level of theory (Table 1; semiempirical calculations are at the x//B3LYP/6-31G(d) level)
Summary
15 16 Vertical, well-to-well, and adiabatic ionization energies (IEs) and electron affinities (EAs) were calculated for the n=1-10 [n]acenes using a wide range of semiempirical, Hartree-Fock, density functional, and second order Moller-Plesset perturbation theory model chemistries. None of the model chemistries examined was able to accurately predict the IEs or EAs for both short- through mid-length [n]acenes, as well as for extrapolations to the polymeric limit, when compared to available experimental and benchmark theoretical data. The poor IE/EA prediction performance for the parent [n]acenes likely extends to their substituted derivatives and heteroatom substituted analogs. Caution should be exercised in the application of non-high level calculations for estimating the IE/EA of these important classes of materials. Caution should be exercised in the application of non-high level calculations for estimating the IE/EA of these important classes of materials. Keywords: [n]acenes; Ionization energies; Electron affinities; Benchmarking; Organic electronics
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
