First-principles study on electronic responses of a C60 molecule to external electric fields

Tsukamoto, Shigeru; Nakayama, Tomonobu; Aono, Masakazu

doi:10.1016/j.chemphys.2007.09.043

Cited by 5 publications

(3 citation statements)

References 29 publications

(29 reference statements)

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“…This result is essentially independent of the alkali atom ionization potential or the number of alkali atoms per C 60 molecule (we tested A x C 60 , where x = 1 and 3). The external doping is ineffective in reducing the SAMO energy because C 60 acts as a Faraday cage; , the collective response of the 240 valence electrons per C 60 molecule effectively screens the states that are confined by the cage from the Coulomb potential of an external charge.…”

Section: Resultsmentioning

confidence: 99%

The Superatom States of Fullerenes and Their Hybridization into the Nearly Free Electron Bands of Fullerites

et al. 2009

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Motivated by the discovery of the superatom states of C60 molecules, we investigate the factors that influence their energy and wave function hybridization into nearly free electron bands in molecular solids. As the n = 3 solutions of the radial Schrodinger equation of the central attractive potential consisting of the short-range C atom core and the long-range collective screening potentials, respectively, located on the icosahedral C60 molecule shell and within its hollow core, superatom states are distinguished by their atom-like orbitals corresponding to different orbital angular momentum states (l = 0, 1, 2,...). Because they are less tightly bound than the pi orbitals, that is, the n = 2 states, which are often exploited in the intermolecular electron transport in aromatic organic molecule semiconductors, superatom orbitals hybridize more extensively among aggregated molecules to form bands with nearly free electron dispersion. The prospect of exploiting the strong intermolecular coupling to achieve metal-like conduction in applications such as molecular electronics may be attained by lowering the energy of superatom states from 3.5 eV for single chemisorbed C60 molecules to below the Fermi level; therefore, we study how the superatom state energies depend on factors such as their aggregation into 1D-3D solids, cage size, and exo- and endohedral doping by metal atoms. We find, indeed, that if the ionization potential of endohedral atom, such as copper, is sufficiently large, superatom states can form the conduction band in the middle of the gap between the HOMO and LUMO of the parent C60 molecule. Through a plane-wave density functional theory study, we provide insights for a new paradigm for intermolecular electronic interaction beyond the conventional one among the sp(n) hybridized orbitals of the organic molecular solids that could lead to design of novel molecular materials and quantum structures with extraordinary optical and electronic properties.

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Section: Resultsmentioning

confidence: 99%

The Superatom States of Fullerenes and Their Hybridization into the Nearly Free Electron Bands of Fullerites

et al. 2009

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“…It can be seen from figure 3 that the length of the S=O bond increases gradually while the length of the S-C bond decreases slightly with increasing external electric field. This change is related to the variation of the internal electric field of the molecule, caused by charge transfer [26]. The atomic properties including atomic charges correlate linearly with the field strengths, but molecular properties present a nonlinear correlation with the external electric field [27].…”

Section: Resultsmentioning

confidence: 99%

Study on the physical and chemical properties of dimethyl sulfoxide under the external electric field

Han,

Feng,

Aizezi

et al. 2023

Phys. Scr.

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Dimethyl sulfoxide (DMSO) is a versatile solvent used in many fields such as medicine and organic synthesis, whereas it is poisonous and harmful to human health. Physical and chemical properties, including bond length, dipole moment, total energy, frontier orbital energy, infrared absorption spectrum as well as the Raman spectrum of the DMSO molecule under an external electric field ranging from 0 to 0.03 atomic units were calculated by using the density functional theory (DFT) with the B3LYP/6-311G++(2d, p) basis set. According to the calculation, it has been found that as the external electric field increases, the two strongest infrared absorption peaks redshift and change in intensity. At the same time, a distinct new characteristic peak emerges in the Raman spectrum when the electric field is applied. Moreover, the Raman characteristic lines of DMSO were detected based on a self-designed Raman spectrometer. The potential energy curves under the increasing electric field were obtained by scanning the single-point energy along the S=O bond with the method B3LYP/6-311G (d, p). By fitting a linear curve between the potential barrier and the electric field, the intensity of the field corresponding to the zero potential barrier was computed. The results provide important theoretical references for further research about the DMSO’s physical and chemical properties and indicate that the structure and properties of molecules change significantly under an external electric field.

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“…In some theoretical studies, the effects induced by an external electric field on molecular and electronic properties have been investigated. These studies have been focusing both on single molecules ,− and on donor−acceptor dyads. , However, cofacial dyads and complexes have not been much studied theoretically under the influence of an external electric field …”

Section: Introductionmentioning

confidence: 99%

Electric-Field-Assisted Electron Transfer in a Porphine−Quinone Complex: A Theoretical Study

Aittala

Cramariuc²,

Hukka

2010

J. Chem. Theory Comput.

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The effects of a static external electric field on the ground state electronic structure of a porphine-quinone (PQ) complex have been studied by using density functional theory (DFT). The energies of the excited states have been calculated with time-dependent density functional theory (TDDFT) and with the approximate coupled cluster singles and doubles (CC2) method. The geometries of porphine and quinone have been optimized with B3LYP. The influence of the external electric field on the PQ complex has been studied at six different intermolecular distances between 2.5 and 5.0 Å with the BH&HLYP functional. An external electric field clearly affects the orbitals localized mostly on quinone but not the orbitals localized on porphine. Additionally, the effect of the external field increases with the increasing intermolecular distance. The optical absorption spectrum of porphine obtained by using the BH&HLYP functional is consistent with the Gouterman model and with the spectrum previously calculated with CAM-B3LYP. The potential energy curves of the Q and B states and the lowest charge transfer (CT) states of the PQ complex calculated by using the BH&HLYP with TDDFT functional have also been compared with those obtained with the CC2 method. Both methods show that the lowest CT state is clearly above the Q states when no external field is applied. Therefore, when the Q states of a porphine-quinone system are excited, the conical intersection is not possible and cannot thus provide a path for electron transfer (ET). The calculations show that the Q and B states are affected by the field much less than the lowest CT state. Consequently, the calculations show that the CT state crosses the Q and B states at certain field strengths. Thus, it is possible that the external electric field triggers ET in porphine-quinone systems via conical intersection.

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First-principles study on electronic responses of a C60 molecule to external electric fields

Cited by 5 publications

References 29 publications

The Superatom States of Fullerenes and Their Hybridization into the Nearly Free Electron Bands of Fullerites

The Superatom States of Fullerenes and Their Hybridization into the Nearly Free Electron Bands of Fullerites

Study on the physical and chemical properties of dimethyl sulfoxide under the external electric field

Electric-Field-Assisted Electron Transfer in a Porphine−Quinone Complex: A Theoretical Study

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