TY - JOUR

T1 - Density Functional Theory Investigation on Boron-Subphthalocyanine

AU - Storm, Freja Eilsø

AU - Hansen, Thorsten

AU - Mikkelsen, Kurt Valentin

PY - 2023

Y1 - 2023

N2 - In this article a Density Functional Theory (DFT) description of derivatives of boron-subphthalocyanines (SubPc) is investigated. Investigated structuresare peripherally functionalized derivatives. It is shown that the generalized gradient functional results of the geometry dier from the geometries foundwith the hybrid functionals, but the deviation is only of the order of a few percent of the total bond lengths for any of the investigated functionals. A linearresponse investigation is also used, where experimental UV-Vis results are compared with computational results. These investigations show that none ofthe investigated functionals are able to compute both peak position of the Q and soret band, but that the functional CAM-B3LYP does give results thatare qualitatively useful, as this is the functional that comes closest to the correct separation of the peaks. A basis set investigation shows little difference inresults within the same functional. To compare results with experimental data, vibornic coupling eects are included using the Franck-Condon, Hertzberg-Teller approximation, and a close resemblance of CAM-B3LYP and experimental results are found. Linear response results found with the functionalsBP86, B3LYP and CAM-B3LYP are also reported for 7 SubPc derivatives, and these show, as has been reported earlier, that peripheral functionalization hasinuence on the frequency and intensity of absorption. These results also show a discrepancy between hybrid functionals and BP86, where BP86 predictstransitions at much lower energies - 300 nm red-shifted compared to the linear response result found with B3LYP and CAM-B3LYP. This is as expectedfor the treatment of charge transfer states with a generalized gradient functional and illustrates why BP86, though suitable for describing the position ofthe Q-band for unfunctionalized SubPc, might not be the best density functional to utilize when investigating SubPc based molecular dyads and triads.

AB - In this article a Density Functional Theory (DFT) description of derivatives of boron-subphthalocyanines (SubPc) is investigated. Investigated structuresare peripherally functionalized derivatives. It is shown that the generalized gradient functional results of the geometry dier from the geometries foundwith the hybrid functionals, but the deviation is only of the order of a few percent of the total bond lengths for any of the investigated functionals. A linearresponse investigation is also used, where experimental UV-Vis results are compared with computational results. These investigations show that none ofthe investigated functionals are able to compute both peak position of the Q and soret band, but that the functional CAM-B3LYP does give results thatare qualitatively useful, as this is the functional that comes closest to the correct separation of the peaks. A basis set investigation shows little difference inresults within the same functional. To compare results with experimental data, vibornic coupling eects are included using the Franck-Condon, Hertzberg-Teller approximation, and a close resemblance of CAM-B3LYP and experimental results are found. Linear response results found with the functionalsBP86, B3LYP and CAM-B3LYP are also reported for 7 SubPc derivatives, and these show, as has been reported earlier, that peripheral functionalization hasinuence on the frequency and intensity of absorption. These results also show a discrepancy between hybrid functionals and BP86, where BP86 predictstransitions at much lower energies - 300 nm red-shifted compared to the linear response result found with B3LYP and CAM-B3LYP. This is as expectedfor the treatment of charge transfer states with a generalized gradient functional and illustrates why BP86, though suitable for describing the position ofthe Q-band for unfunctionalized SubPc, might not be the best density functional to utilize when investigating SubPc based molecular dyads and triads.

U2 - 10.47363/JNSRR/2023(5)152

DO - 10.47363/JNSRR/2023(5)152

M3 - Journal article

VL - 5

SP - 1

EP - 10

JO - Journal of Nanosciences Research & Reports

JF - Journal of Nanosciences Research & Reports

SN - 2754-4966

IS - 3

ER -