Ab initio calculations of the polarizability and the hyperpolarizability of C60

Abstract

The linear polarizability, α, and the second hyperpolarizability, γ, of C60 in gas phase have been computed by ab initio cubic response theory in the random phase approximation and with an efficient parallel implementation. With a tailored, well-tested, basis set, containing more than 1000 contracted basis functions the average values of α and γ are predicted to be 8.58×10−23 cm3 and 5.73×10−35 esu, respectively, which are about 8 and 9 times larger than the corresponding values for benzene calculated at the same level of accuracy.

[60]Fullerene as a Substituent

“…Conversely, their polarizabilities (a) are substantially different: an HF/3-21G calculation yields average volume polarizabilities of a 88 and 24 ä 3 for 1 and 2, respectively (the value for 1 compares favorably with the value for C 60 itself, a 86 ä 3 ). [19] The polarizability of water (1.45 ä 3 ) is also substantially smaller than that of 1-octanol (17 ä 3 , estimated from that of di-nbutyl ether [20] ). From the classical expression for the dispersive interaction of two spherical particles with given a and ionization potential I, [Eq.…”

Accurate density functional calculations on frequency-dependent hyperpolarizabilities of small molecules

“…Although there is a large scatter in both the experimental and theoretical results, there seems to be a growing consensus on both the theoretical 5,17 and experimental 16,18 sides that the hyperpolarizability of C 60 is much smaller than initially thought.…”

Time-dependent density functional study of the static second hyperpolarizability of BB-, NN- and BN-substituted C60

“…Also presented in Table 3 are three recent theoretical predictions of the second hyperpolarizablility of C 60 . A comparison with experiments are difficult due to the large differences in the experimental results [5][6][7] and the comparison will therefore only be made with theoretical results. In this work we have neglected vibrational, dispersion and solvent effect and these factors have to be considered when comparing with experiments.…”

“…Recently both experiments [3,4] and theory [5][6][7] have shown that the third-order nonlinearity of C 60 is smaller than first assumed. For this reason the third-order nonlinearity of derivatives of C 60 have been experimentally investigated and found to provide a large increase in the nonlinearity compared with the pure C 60 , see e.g.…”

“…These studies have been done using an extended Su-Schrieffer-Heeger (SSH) model [11] and show that doping enlarges the second hyperpolarizability by several orders of magnitude compared to the pure fullerenes, suggesting B-, N-, and BN-doped fullerenes as serious candidates for photonic devices. Since the SSH model predicts results [9] for the pure fullerene which are larger than that predicted with first-principle methods www.elsevier.com/locate/cplett such as DFT and ab initio SCF [5][6][7] it is interesting also to investigate the effects of substitutedoping on the second hyperpolarizability of the fullerenes using DFT.…”