Tunneling Motion and Antiferroelectric Ordering of Lithium Cations Trapped inside Carbon Cages

Aoyagi, Shinobu; Tokumitu, Akio; Sugimoto, Kunihisa; Okada, Hiroshi; Hoshino, Norihisa; Akutagawa, Tomoyuki

doi:10.7566/jpsj.85.094605

Cited by 28 publications

(44 citation statements)

References 23 publications

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“…The Li + position is beneath the centre of a hexagon of the C 60 with the major orientation, as shown in figure 1 e . The average Li + –C distance is 2.35(10) Å, which agrees with the value for [Li + @C 60 ](PF 6 − ) at low temperature [18,19]. Assuming that the site occupancy for the Li + position is the same as that of the major C 60 orientation (0.372(5)), the isotropic atomic displacement parameter of the Li + is refined to 0.24(3) Å 2 , and the remaining fraction of the Li + cation would occupy other positions inside the C 60 by a positional disorder.…”

Section: Resultssupporting

confidence: 84%

“…The value at 100 K is obviously shorter than the Li + –C distance of 2.37(1) Å in [Li + @C 60 ](PF 6 − ) at 40 K [19]. It is also noted that the Li + cation in the (Li + @C 60 − ) 2 dimer locates near the centre of a pentagon involving C2, as shown in figure 4 d,e , while the Li + cation in [Li + @C 60 ](PF 6 − ) locates near the centre of the hexagons [18,19]. The formation of the shorter Li + –C bond contributes to stabilization of the (Li + @C 60 − ) 2 dimer.…”

Section: Resultsmentioning

confidence: 99%

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Structure of [60]fullerene with a mobile lithium cation inside

et al. 2018

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The structure of crystalline [60]fullerene with a lithium cation inside (Li+@C60) was determined by synchrotron radiation X-ray diffraction measurements to understand the electrostatic and thermal properties of the encapsulated Li+ cation. Although the C60 cages show severe orientation disorder in [Li+@C60](TFPB−)·C4H10O and [Li+@C60](TFSI−)·CH2Cl2, the Li+ cations are rather ordered at specific positions by electrostatic interactions with coordinated anions outside the C60 cage. The Li+@C60 molecules in [Li+@C60](ClO4−) with a rock-salt-type cubic structure are fully disordered with almost uniform spherical shell charge densities even at 100 K by octahedral coordination of ClO4− tetrahedra and show no orientation ordering, unlike [Li+@C60](PF6−) and pristine C60. Single-bonded (Li+@C60−)2 dimers in [Li+@C60−](NiOEP)⋅CH2Cl2 are thermally stable even at 400 K and form Li+–C bonds which are shorter than Li+–C bonds in [Li+@C60](PF6−) and suppress the rotational motion of the Li+ cations.

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Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 99%

Structure of [60]fullerene with a mobile lithium cation inside

et al. 2018

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“…TDDFT calculations show the sensitivity of the electronic binding energies on the position of the Li that is expected to be highly mobile under the conditions of the gas phase experiments. 23 The low temperature STM/STS studies, for which the Li is static, show a strong interaction between the SAMO states and the metal substrate, moving the binding energies for the S-and P z -SAMO significantly closer to the Fermi energy.…”

Section: Introductionmentioning

confidence: 99%

Angle-resolved photoelectron spectroscopy and scanning tunnelling spectroscopy studies of the endohedral fullerene Li@C₆₀

et al. 2019

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Angle-resolved photoelectron spectroscopy and scanning tunnelling spectroscopy studies of the endohedral fullerene Li@C 60 .Gas phase photoelectron spectroscopy, TD-DFT calculations and low temperature UHV STM experiments are combined to provide information about the infl uence of the encapsulated Li on the symmetry and energetics of the low lying diff use Super-Atom Molecular Orbitals (SAMOs) of Li@C 60 . PAPER Yao Cai, Yongxin Pan et al. Positive magnetic resonance angiography using ultrafi ne ferritin-based iron oxide nanoparticles Nanoscale rsc.li/nanoscale Volume Gas phase photoelectron spectroscopy (Rydberg Fingerprint Spectroscopy), TDDFT calculations and low temperature STM studies are combined to provide detailed information on the properties of the diffuse, low-lying Rydberg-like SAMO states of isolated Li@C 60 endohedral fullerenes. The presence of the encapsulated Li is shown by the calculations to produce a significant distortion of the lowest-lying S-and P-SAMOs that is dependent on the position of the Li inside the fullerene cage. Under the high temperature conditions of the gas phase experiments, the Li is mobile and able to access different positionswithin the cage. This is accounted for in the comparison with theory that shows a very good agreement of the photoelectron angular distributions, allowing the symmetry of the observed SAMO states to be identified. When adsorbed on a metal substrate at low temperature, a strong interaction between the lowlying SAMOs and the metal substrate moves these states to energies much closer to the Fermi energy compared to the situation for empty C 60 while the Li remains frozen in an off-centre position. † Electronic supplementary information (ESI) available: Temperature-dependent mass spectrometry, laser power ionisation dependence and STM imaging details.

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“…The EMFs show enhanced reactivity not only towards Diels-Alder [36] but also to other essential reactions necessary for varied utilization [37] . In this regard, Li + encapsulated fullerenes (Li + @C 60 ) [38,39 ] are of great interest for both experimentalists as well as theoreticians. According to the studies done by Ueno et al [40 ] , a lesser HOMO-LUMO gap in Li + @C 60 compared to neutral C 60 is the principal reason for facilitating [4+2] cycloaddition reaction, inducing significant changes in the frontier orbitals.…”

Section: Introductionmentioning

confidence: 99%

Computational insights into the Multi-Diels-Alder reactions of neutral C60 and its Li+ encapsulated analogue: A DFT study

Ash

Banerjee

Debnath

et al. 2021

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Diels-Alder cycloaddition reaction is helpful to produce covalent derivatives of fullerene with desirable electronic and physical properties. In the present venture, we have computationally investigated the reactivity of neutral C and its Li encapsulated derivative towards Multi-Diels-Alder (MDA) reaction with 1,3-butadiene, employing density functional theory (DFT). The computational reports available to date illustrate the functionalization of fullerene surfaces of neutral and encapsulated C (Ca and Sm) with two butadiene molecules. In this article, we aim to investigate whether more than two butadiene molecules can be attached to the fullerene surface or not. To do so, we have shown that the MDA reaction initiates with the formation of an encounter complex between the mono-functionalized fullerene product and the second butadiene molecule. In this context, two different approaches, namely ‘Direct’ and ‘Alternative’ have been considered based on the attachment of the second butadiene, i.e., whether it is attached to the opposite or adjacent position of the first functionalization, which eventually produces the same final product. We have explored the MDA reactions by considering a total of four diene molecules that can be embedded successfully on the fullerene surface, with each reaction step having a high degree of exothermicity, thus making the overall reaction thermodynamically facile. In harmony with the mono- and bis-cycloaddition reactions, for MDA reaction also, the positive impact of Li encapsulation for enhancing the reactivity of fullerene surface towards butadiene attachment is evident from our study. On-the-fly calculations also suggest the bond preference for [6, 6] connectivity than its [6, 5] counterpart, to be the suitable dienophile, just like the mono- and bis-functionalization reported earlier. Overall, the present study will foresee an extensive idea about the detailed mechanism of the MDA reaction on neutral C and Li@C that could encourage the scientists to perform the aforementioned reaction for other fullerene derivatives in the long run.

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Tunneling Motion and Antiferroelectric Ordering of Lithium Cations Trapped inside Carbon Cages

Cited by 28 publications

References 23 publications

Structure of [60]fullerene with a mobile lithium cation inside

Structure of [60]fullerene with a mobile lithium cation inside

Angle-resolved photoelectron spectroscopy and scanning tunnelling spectroscopy studies of the endohedral fullerene Li@C₆₀

Computational insights into the Multi-Diels-Alder reactions of neutral C60 and its Li+ encapsulated analogue: A DFT study

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Tunneling Motion and Antiferroelectric Ordering of Lithium Cations Trapped inside Carbon Cages

Cited by 28 publications

References 23 publications

Structure of [60]fullerene with a mobile lithium cation inside

Structure of [60]fullerene with a mobile lithium cation inside

Angle-resolved photoelectron spectroscopy and scanning tunnelling spectroscopy studies of the endohedral fullerene Li@C60

Computational insights into the Multi-Diels-Alder reactions of neutral C60 and its Li+ encapsulated analogue: A DFT study

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Angle-resolved photoelectron spectroscopy and scanning tunnelling spectroscopy studies of the endohedral fullerene Li@C₆₀