Communication: A density functional investigation of structure-property evolution in the tetrakis hexahedral C4Al14 nanocluster

Irving, Benjamin J.; Naumkin, Fedor Y.

doi:10.1063/1.4897259

Cited by 3 publications

(6 citation statements)

References 27 publications

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“…The EA values change rather weakly (within 10%) from that for isolated cubic C 8 (2.90 eV) upon its encapsulation in the Al n cage or upon its attachment to Al n (c) , even though these species have comparable EA values of their own. This is similar to the case of C 4 @Al 14 . For the Al n cage and Al n (c) isomers, the EA values are slightly larger or smaller, respectively, than that for C 8 .…”

Section: Resultssupporting

confidence: 78%

“…Relative to the cage isomers plus relaxed cubic C 8 , the C 8 @Al 16 and C 8 @Al 18 systems are calculated to be stable by about 5.5 and 6.0 eV, respectively. These are larger than about 4.1 eV for C 4 @Al 14 , in agreement with more C–Al interactions. These D e values are about 7 to 8 times smaller than those for the dissociation of the aluminum cages, which is close to a factor of about 8.5 for the case of C 4 @Al 14 .…”

Section: Resultssupporting

confidence: 62%

“…Structures and Stabilities. Previously, 14 the C 4 @Al 14 cluster was stabilized as a C 4 square inside a nearly cubic Al 8 cage with each of its six faces capped by another Al atom. The near cube had Al atoms bridging each C−C bond (side of the square) above and under the C 4 plane.…”

Section: Resultsmentioning

confidence: 99%

“…This was followed by an increase in the shell size in order to complete and symmetrize it as in C 4 @Al 14 . 14 In particular, for this system the ionization energy and electron affinity were found to be rather invariable upon insertion of the carbon core. Furthermore, on the mesoand macroscales, relevant systems included CAl n mono-layers 15,16 and carbon-nanofiber-hardened aluminum.…”

Section: Introductionmentioning

confidence: 84%

“…In further work, in order to reach beyond the relatively well-studied systems with monatomic doping, the carbon-core size inside the (icosahedral) Al 12 shell was systematically increased up to C 4 , eventually altering the shell symmetry. This was followed by an increase in the shell size in order to complete and symmetrize it as in C 4 @Al 14 . In particular, for this system the ionization energy and electron affinity were found to be rather invariable upon insertion of the carbon core.…”

Section: Introductionmentioning

confidence: 89%

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Shape Symmetrization and IR-Spectral Enhancement of Aluminum Clusters via Doping with a Carbon Core

Naumkin

2021

J. Phys. Chem. A

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Composite nanosystems are a class of objects with interesting and potentially useful properties. Here we study mixedcomposition species representing interfaces at the molecular level between such technologically relevant materials as carbon and aluminum. Specifically, core−shell C 8 @Al n (n = 16, 18) species and their isomers with the core and relaxed-shell attached outside are investigated at a DFT level in terms of structures and stabilities, charge distributions and polarities, and IR spectra and electron affinities. Among the interesting findings is the possibility of bringing the aluminum cluster into a more symmetric shape (thus making a convenient building block) via insertion of a suitable molecular-carbon skeleton. Another notable feature is the systemselective dependence of polarity on spin multiplicity, suggesting possible molecular−electronic applications. The IR spectra of the composite species are much brighter compared to those of the separated components and are highly focused for the core−shell isomers. A related aspect of interest is the apparent reflections of the system structural details in the IR spectra features (line intensities and separations) via related vibrations, facilitating an experimental analysis of the structure and detection of the species formation and transformation as well as potentially enabling the means of achieving desirable optical characteristics via a geometric design.

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Section: Resultssupporting

confidence: 78%

Section: Resultssupporting

confidence: 62%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 84%

Section: Introductionmentioning

confidence: 89%

See 3 more Smart Citations

Shape Symmetrization and IR-Spectral Enhancement of Aluminum Clusters via Doping with a Carbon Core

Naumkin

2021

J. Phys. Chem. A

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Structural and bonding properties of AlnC4−/0 (n = 2–4) clusters: Anion photoelectron spectroscopy and theoretical calculations

Zhang

Yan

et al. 2021

Chinese Journal of Chemical Physics

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We measured the photoelectron spectra of AlnC4− (n=2-4) clusters by using size-selected anion photoelectron spectroscopy. The structures of AlnC4−/0 (n = 2–4) clusters were explored with quantum chemistry calculations and were determined by comparing the theoretical results with the experimental spectra. It is found that the most stable structure of Al2C4− anion is a C2v symmetry planar structure with two Al atoms interacting with two C2 units. In addition, Al2C4− anion also has a D∞h symmetry linear structure with two Al atoms located at the two ends of a C4 chain, which is slightly higher in energy than the planar structure. The most stable structure of neutral Al2C4 has a D∞h symmetry linear structure. The most stable structure of Al3C4− anion is a planar structure with three Al atoms interacting with two C2 units. Whereas neutral Al3C4 cluster has a C2v symmetric V-shaped bent structure. The global minima structures of both Al4C4− and neutral Al4C4 are C2h symmetry planar structures with four Al atoms interacting with the ends of two C2 units. Adaptive natural density partitioning analyses of AlnC4− (n=2−4) clusters show that the interactions between the Al atoms and C2 units have both σ and π characters.

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Al2C4H2 Isomers with the Planar Tetracoordinate Carbon (ptC)/Aluminum (ptAl)

Malhan

Sobinson

Job

et al. 2022

Atoms

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Forty-one isomers of Al2C4H2 that lie within 50 kcal mol−1 are theoretically identified in this work using density functional theory. Among these, isomers 3 and 14 contain a planar tetracoordinate carbon (ptC) atom that lies at 3.3 and 16.9 kcal mol−1, respectively, and are above the global minimum geometry 1 at the ωB97XD/6-311++G(2d,2p) level of theory. The other ten isomers that also contain unique bonding features are isomers 4, 18, 20, 21, 22, 27, 28, 31, 34, and 40. Out of these isomers, 4, 18, 20, 22, 27, 28, and 34 contain planar tetracoordinate aluminum (ptAl) whereas isomers 31 and 40 contain both ptC and ptAl atoms. Chemical bonding characteristic features are thoroughly analyzed for all these eleven isomers with various bonding and topological quantum chemical tools, such as NBO, AdNDP, WBI, and ELF, except isomer 27 due to the observed elongated Al-Al bond length. The current results indicate that ptC isomer 3 is more stable than other isomers because electron delocalization is more prevalent and it also has double aromaticity as observed from the ELF, NICS, and AdNDP analysis. Further, the structural stability of these isomers is investigated through ab initio molecular dynamics (AIMD) simulation. Isomer 21 shows the planar pentacoordinate aluminum but it is observed as a kinetically unstable geometry from AIMD and, further, one could notice that it isomerizes to isomer 12.

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Communication: A density functional investigation of structure-property evolution in the tetrakis hexahedral C4Al14 nanocluster

Cited by 3 publications

References 27 publications

Shape Symmetrization and IR-Spectral Enhancement of Aluminum Clusters via Doping with a Carbon Core

Shape Symmetrization and IR-Spectral Enhancement of Aluminum Clusters via Doping with a Carbon Core

Structural and bonding properties of AlnC4−/0 (n = 2–4) clusters: Anion photoelectron spectroscopy and theoretical calculations

Al2C4H2 Isomers with the Planar Tetracoordinate Carbon (ptC)/Aluminum (ptAl)

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