Small carbides of third-row main group elements: structure and bonding in C3X compounds (X = K–Br)

Villanueva, Estefanía Fernández; Rayón, Víctor M.; Barrientos, Carmen; Largo, Antonio

doi:10.1039/c2cp41762f

Cited by 5 publications

(3 citation statements)

References 64 publications

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“…In the case of UC 3 , a similar behavior was observed: 11 the fan isomer was also predicted as the global minimum. In addition, a systematic study of third row main group tricarbides 32 has shown that fan or rhombic isomers are favored for less electronegative elements, whereas for more electronegative elements, three-membered rings or linear species are preferred. Uranium and plutonium, both having low electronegativities, behave like electropositive atoms such as K or Ca rather than like electronegative atoms such as Se or Br.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Molecular Structure and Bonding in Plutonium Carbides: A Theoretical Study of PuC₃

et al. 2016

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The most relevant species of plutonium tricarbide were characterized using theoretical methods. The global minimum is predicted to be a fan structure where the plutonium atom is bonded to a quasi-linear C 3 unit. A rhombic isomer, shown to be a bicyclic species with transannular C−C bonding, lies about 39 kJ/mol above the fan isomer. A linear PuCCC isomer and a three-membered ring CPuC 2 isomer were found to be higher in energy (150 and 195 kJ/ mol, respectively, above the predicted global minimum). The possible processes for the formation of these species are discussed, and the IR spectra were predicted to help in possible experimental detection. The nature of the Pu−C interaction has been analyzed in terms of a topological analysis of the electronic density, showing that Pu−C bonding is essentially ionic with a certain degree of covalent character. 51 out recently. 9−11 An important conclusion from these studies is 52 that the most stable species is not always observed in the 53 experiments. For example, the linear uranium dicarbide 54 observed in the experiments, 6,7 CUC, is not the lowest-lying 55 isomer of uranium dicarbide. The global minimum is predicted 56 to be a C 2v-symmetric (T-shape) U(C 2) isomer, with an energy 57 lying more than 240 kJ/mol lower than that of the linear 58 species. 7,9,10 Recent theoretical studies on uranium dicarbide 59 include the adsorption of the linear and T-shape uranium 60 dicarbide isomers on a graphene surface. 12 Other studies on 61 actinide carbides include a very recent work on NpC, NpC 2 , 62 and NpC 4. 13 63 On the other hand, little is known about the molecular 64 structure of small plutonium carbides. Datta et al. 5 observed 65 PuC n + ions through radio-frequency spark source mass 66 spectrometry studies, but no structural information is available 67 from these experiments. In a recent study by Pogany et al., 14 68 triangular PuC 2 was predicted from theoretical calculations to 69 lie about 381 kJ/mol below CPuC in energy. The molecular 70 structure of PuC 4 has also been theoretically studied in another 71 paper by Pogany et al., 15 which predicted a fan-type structure as 72 the most stable isomer. To the best of our knowledge, no 73 information is available for other plutonium carbides. In the 74 present work, a theoretical study of the next member in this 75 series is provided. The aim of the present work was to

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Section: ■ Results and Discussionmentioning

confidence: 99%

Molecular Structure and Bonding in Plutonium Carbides: A Theoretical Study of PuC₃

et al. 2016

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“…In a systematic study of small carbides for third-row main group elements, 29 it was found that the more electronegative elements (As, Se, Br) favor linear or threemembered ring structures, whereas less electronegative elements (K, Ca, Ga, Ge) clearly prefer either fan or rhombic isomers. Uranium, with low ionization energy, behaves in a similar way as other electropositive elements such as K or Ca.…”

Section: Resultsmentioning

confidence: 99%

Molecular structure of uranium carbides: Isomers of UC3

Zalazar

Rayón

Largo

2013

The Journal of Chemical Physics

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In this article, the most relevant isomers of uranium tricarbide are studied through quantum chemical methods. It is found that the most stable isomer has a fan geometry in which the uranium atom is bonded to a quasilinear C 3 unit. Both, a rhombic and a ring CU(C 2 ) structures are found about 104-125 kJ/mol higher in energy. Other possible isomers including linear geometries are located even higher. For each structure, we provide predictions for those molecular properties (vibrational frequencies, IR intensities, dipole moments) that could eventually help in their experimental detection. We also discuss the possible routes for the formation of the different UC 3 isomers as well as the bonding situation by means of a topological analysis of the electron density.

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“…In organometallics, the C 3 Se species has been used as a bridging ligand [27]. Some previous information on carbon-selenium species has been obtained from quantum-chemical calculations, albeit at rather modest levels of theory [26,[28][29][30][31][32].…”

Section: Introductionmentioning

confidence: 99%

Experimental and quantum-chemical characterization of heavy carbon subchalcogenides: Infrared detection of SeC$_3$Se

Salomon,

Dudek,

Chernyak

et al. 2021

Preprint

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High-resolution infrared studies of laser ablation products from carbon-selenium targets have revealed a new vibrational band at 2057 cm −1 that is identified as the ν 3 vibrational fundamental of the SeC 3 Se cluster. Because of the rich isotopic composition of selenium and the heavy nuclear masses involved, the vibrational band shows a relatively compact and complex structure despite the simple linear geometric arrangement. Overall, rotationalvibrational lines of six isotopologues could be assigned and fitted permitting the derivation of an accurate selenium-carbon bond length. Spectroscopic analysis has been greatly supported by high-level quantumchemical calculations of the molecular structure and the harmonic and anharmonic force fields performed at the CCSD(T) level of theory. Scalarrelativistic effects on the molecular structure were also considered but found of little importance.

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Small carbides of third-row main group elements: structure and bonding in C3X compounds (X = K–Br)

Cited by 5 publications

References 64 publications

Molecular Structure and Bonding in Plutonium Carbides: A Theoretical Study of PuC₃

Molecular Structure and Bonding in Plutonium Carbides: A Theoretical Study of PuC₃

Molecular structure of uranium carbides: Isomers of UC3

Experimental and quantum-chemical characterization of heavy carbon subchalcogenides: Infrared detection of SeC$_3$Se

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Small carbides of third-row main group elements: structure and bonding in C3X compounds (X = K–Br)

Cited by 5 publications

References 64 publications

Molecular Structure and Bonding in Plutonium Carbides: A Theoretical Study of PuC3

Molecular Structure and Bonding in Plutonium Carbides: A Theoretical Study of PuC3

Molecular structure of uranium carbides: Isomers of UC3

Experimental and quantum-chemical characterization of heavy carbon subchalcogenides: Infrared detection of SeC$_3$Se

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Molecular Structure and Bonding in Plutonium Carbides: A Theoretical Study of PuC₃

Molecular Structure and Bonding in Plutonium Carbides: A Theoretical Study of PuC₃