Defect Induced Electronic Structure of Uranofullerene

Dai, Xing; Cheng, Cheng; Zhang, Wei; Xin, Minsi; Huai, Ping; Zhang, Ruiqin; Wang, Jianpeng

doi:10.1038/srep01341

Cited by 32 publications

(38 citation statements)

References 54 publications

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“…The choice of PBE functional is based on some previous reports. 76 −78 The structural and energy trends obtained using PBE functional are found to be the same as obtained using the B3LYP functional, with a slight decrease in the total energy values in case of PBE functional as compared to the B3LYP functional. The relative energy trends using PBE functional are reported in Table 1.…”

Section: Resultssupporting

confidence: 59%

Enhancement in the Stability of 36-Atom Fullerene through Encapsulation of a Uranium Atom

Manna

Ghanty

2013

J. Phys. Chem. C

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With an objective to rationalize the experimentally observed intense U@C 36 peak in the mass spectrum of U@C 2n metallofullerene, structural, stability, and spectroscopic aspects of the uranium doped C 36 fullerene have been studied in a unified and systematic way using density functional theory (DFT) and its time-dependent variant. Relativistic effects have been taken into account within the framework of zeroth-order regular approximation using scalar and spin− orbit-based approaches. Among all of the 15 possible classical isomers reported for the C 36 fullerene cage system, singlet D 2d and triplet D 6h structures are found to be isoenergetic and most stable. Encapsulation of uranium atom into various C 36 cages leads to 15 distinct isomers with considerable energy differences. It has also been shown that this encapsulation process results in significant gain in thermodynamic stability. The most stable U@C 36 isomer is found to be associated with C 6v symmetry and closed-shell electronic configuration, derived from the open-shell D 6h structure of C 36 . The next stable isomer is associated with C s symmetry and obtained from the corresponding singlet D 2d structure of the C 36 cage. Distinct changes have also been found in the calculated vibrational and UV−visible spectra of the U@C 36 cluster as compared to the corresponding bare C 36 cage. All of the calculated quantities reported here suggest that the stability of the U@C 36 cluster is high enough for possible formation of cluster-assembled material leading to synthesis of this metallofullerene experimentally.

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Section: Resultssupporting

confidence: 59%

Enhancement in the Stability of 36-Atom Fullerene through Encapsulation of a Uranium Atom

Manna

Ghanty

2013

J. Phys. Chem. C

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“…Furthermore, in order to examine the reliability of the exchange-correlation functional and basis set, we calculated the structures of Au 2 and U 2 dimers, and the zirconium-encapsulated nano-cage Zr@Au 14 cluster. All the results qualitatively agree with the previous reports413143738394041. The details for these calculations have been presented in the SI Part 4.…”

Section: Resultssupporting

confidence: 90%

“…The reason why the ground state of the U@Au 14 structure is triplet is that the two unpaired electrons on the U atoms exist in the form of parallel spin. Through these analyses, we can confirm that the U@Au 14 structure is different from ordinary systems of which the inner metal and outer shell participate jointly in the electronic state adjustment, such as U 2 @C 61 14, instead it is a system of uranium self-induced electronic spin state after electron transfer between them within the confinement. Meanwhile, the U@Au 14 nanostructure displays some unique electronic properties with the encapsulated metal atom gaining electrons and the outer cluster losing them, while the majority of such nanostructures show the opposite electron transfers141516.…”

Section: Resultsmentioning

confidence: 85%

“…With DFT, electron correlations can be handled effectively without significantly increasing the computational complexity, as demonstrated in its wide applications in actinides and related systems14515253. Similarly, for gold clusters, the DFT method seems to work very well5455.…”

Section: Methodsmentioning

confidence: 99%

“…B3LYP) is computationally unbearable60, we performed the single-point energy calculations at B3LYP level based on the PBE geometry, which is similar to a previous approach by Dognon et al61. Atomic partial charges were calculated similar to previous reports using the Mulliken population analysis14. Single-electron wave functions were expanded using the TZ2P (a triple-ζ basis set with two sets of polarization functions) uncontracted Slater-type orbital (STO) basis set for all atoms62.…”

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Structural and electronic properties of uranium-encapsulated Au14 cage

Dai

Kang

Jimenez-Cruz

et al. 2014

Sci Rep

Self Cite

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The structural properties of the uranium-encapsulated nano-cage U@Au14 are predicted using density functional theory. The presence of the uranium atom makes the Au14 structure more stable than the empty Au14-cage, with a triplet ground electronic state for U@Au14. Analysis of the electronic structure shows that the two frontier single-occupied molecular orbital electrons of U@Au14 mainly originate from the 5f shell of the U atom after charge transfer. Meanwhile, the bonding orbitals and charge population indicate that the designed U@Au14 nano-cage structure is stabilized by ionocovalent interactions. The current findings provide theoretical basis for future syntheses and further study of actinide doped gold nanoclusters, which might subsequently facilitate applications of such structure in radio-labeling, nanodrug carrier and other biomedical applications.

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Unraveling the Electronic Structure, Spin States, Optical and Vibrational Spectra of Malaria Pigment

Ali

Oppeneer

2015

Chemistry A European J

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A detailed knowledge of the electronic structure and magnetic and optical properties of hemozoin, the malaria pigment, is essential for the design of effective antimalarial drugs and malarial diagnosis. By employing state-of-the-art electronic structure calculations, we have performed an in-depth investigation of the malaria pigment. Specifically, molecular bond lengths and spin states of the two Fe(III) heme centers and their exchange interaction, the UV/Vis absorption spectrum, and the IR vibrational spectra were calculated and compared with available experimental data. Our density functional theory (DFT)-based calculations predict a singlet ground spin state that stems from an S=5/2 spin state on each of the Fe heme centers with a very weak antiferromagnetic exchange interaction between them. Our theoretical UV/Vis and IR spectra provide explanations for various spectroscopic studies of hemozoin and β-hematin (a synthetic analogue of hemozoin). A good comparison of calculated and measured properties demonstrates the convincing unveiling of the electronic structure of the malaria pigment. Based on the predicted vibrational spectra, we propose a unique spectral band from the nuclear resonance vibrational spectroscopy (NRVS) results that could be used as a key fingerprint for malarial detection.

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Defect Induced Electronic Structure of Uranofullerene

Cited by 32 publications

References 54 publications

Enhancement in the Stability of 36-Atom Fullerene through Encapsulation of a Uranium Atom

Enhancement in the Stability of 36-Atom Fullerene through Encapsulation of a Uranium Atom

Structural and electronic properties of uranium-encapsulated Au14 cage

Unraveling the Electronic Structure, Spin States, Optical and Vibrational Spectra of Malaria Pigment

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