General formula for accurate calculation of halofullerenes polarizability

Polarizability as a landmark property for fullerene chemistry and materials science

“…141 In our works, we have theoretically investigated mean polarizabilities of the positional isomers of C 60 X 2 with the simplest addends by PBE/3z method. 8,53,132 As it turned out, mean polarizabilities of isomeric bisepoxy-, bisaziridino-and biscyclopropa [60]fullerenes (X ¼ O, NH, and CH 2 , respectively) are approximately equal ($84, $86 and $87 Å3 , respectively). This rule holds true for [2 + 3]-and [2 + 4]-adducts of C 60 (ref.…”

“…High a values of fullerenes have been used to qualitatively explain the distinctiveness of physicochemical processes in fullerene-containing systems such as the anomalously effective quenching of electronically-excited states of organic compounds by C 60 and C 70 , 44 propensity of fullerenes for aggregation, 73 formation of the donor-acceptor complexes, 74 and behavior of the atoms, encapsulated by fullerene cages ), 35 75.1 (HF/6-31 ++G), 36 83.0 (topological model), 39 77.5 (point dipole interaction model), 40 75.7 (bond order model), 41 82.7 (PBE/3z), 45 82.1 (PBE/ NRLMOL), 46 82.9 (QSRP model), 49 81.6 (PBE0/ SVPD), 51 78.4 (VWN/DZVP/GEN-A2), 52 80.3 (B3LYP/L1), 53 78.4 (M06-2X/6-31+G(d,p), 55 71.7 (B3LYP/6-31G(d)) 56 76.5 AE 8.0 (molecular beam deection), 22,38 79.0 AE 6.0 (time-of-ight technique), 37 88.9 AE 6.0 (interferometry) 42 C 70 (D 5h ) 93.2 (CPHF/(7s4p)[3s2p]), 35 89.8 (HF/6-31 ++G), 36 88.3 (bond order model), 41 103.0 (PBE/ NRLMOL), 43 102.7 (PBE/3z), 44 93.6 (QSRP model), 49 97.8 (VWN/DZVP/GEN-A2), 52 100.7 (B3LYP/L1) 53 101.9 AE 13.9 (molecular beam deection), 38 (including their photoionization 76 ). For example, Bulgakov and Galimov have discovered that C 70 is substantially more effective quencher from electronically excited states owing to energy transfer than C 60 .…”

“…Polarizability of fullerene derivatives has been studied mainly by theoretical techniques 8,53,56,92,[123][124][125][126][127][128][129][130][131][132][133][134][135][136][137] because of many reasons such as their possible dissociation under experiments, low solubility, and low availability. The only experimental work in this eld deals with the optical polarizabilities of polyuoro [60] fullerenes measured by Tau-Talbot-Kapitza-Dirac interferometry.…”

“…138 As is known from the theoretical studies, mean polarizabilities of exohedral fullerene derivatives are higher than the polarizability of the original fullerene if its carbon framework does not degrade upon chemical functionalization. 8,53,56,92,[123][124][125][126][127][128][129][130][131][132][133][134][135][136][137] This is true for both mono-and polyadducts, produced by [ 8,53,56,92,123,[125][126][127][128]131,132,134,135 C 70 , 53,131,133,136,137 C 50 , 124 or C 56 (ref. 130) fullerenes.…”

The impact of chemical structure and molecular packing on the electronic polarisation of fullerene arrays

“…In this paper, we examine independently the effect of chemical structure and molecular packing on the energetics in finite molecular crystals. We select fullerenes for this study, owing to their widespread use in organic photovoltaic devices, their crystalisability (and availability of solved crystal structures), their symmetry and the near isotropic nature of their molecular polarisability [38][39][40] , and the range of functionalised forms available, giving rise to different molecular polarisabilities and packing motifs. The high polarisability of fullerene molecules has also been ascribed an important role in generating free charges 41 , as has the rapid delocalisation of the electron within fullerene crystallites or highly ordered fullerene domains [42][43][44] .…”