Theoretical study of Pu and Am tetracarbide molecules

Pogány, Péter; Kovács, Attila; Konings, R.J.M.

doi:10.1002/qua.24628

Cited by 9 publications

(7 citation statements)

References 49 publications

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“…In a recent study by Pogany et al, triangular PuC 2 was predicted from theoretical calculations to lie about 381 kJ/mol below CPuC in energy. The molecular structure of PuC 4 has also been theoretically studied in another paper by Pogany et al, which predicted a fan-type structure as the most stable isomer. To the best of our knowledge, no information is available for other plutonium carbides.…”

Section: Introductionmentioning

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: Introductionmentioning

confidence: 99%

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

et al. 2016

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“…Yet, only four theoretical studies dealt with AnC molecules (UC, 19,20 NpC, 21 and PuC 22 ) until now, providing very limited information on their molecular properties. In contrast, the di-, 21,[23][24][25][26] tri-, 27,28 and tetracarbides 18,20,21,29 of Th, U, Np, Pu, and Am have been quite extensively explored by advanced quantum chemical calculations. The lack of reliable information on the monocarbides is the motivation to our present study in which we apply relativistic multireference and density functional theory (DFT) methods to elucidate the electronic structure and other molecular characteristics of the most important monocarbides (ThC, UC, PuC, and AmC).…”

Section: Introductionmentioning

confidence: 99%

Theoretical study of actinide monocarbides (ThC, UC, PuC, and AmC)

Pogány

Kovács

Visscher

et al. 2016

The Journal of Chemical Physics

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A study of four representative actinide monocarbides, ThC, UC, PuC, and AmC, has been performed with relativistic quantum chemical calculations. The two applied methods were multireference complete active space second-order perturbation theory (CASPT2) including the Douglas-Kroll-Hess Hamiltonian with all-electron basis sets and density functional theory with the B3LYP exchange-correlation functional in conjunction with relativistic pseudopotentials. Beside the ground electronic states, the excited states up to 17 000 cm−1 have been determined. The molecular properties explored included the ground-state geometries, bonding properties, and the electronic absorption spectra. According to the occupation of the bonding orbitals, the calculated electronic states were classified into three groups, each leading to a characteristic bond distance range for the equilibrium geometry. The ground states of ThC, UC, and PuC have two doubly occupied π orbitals resulting in short bond distances between 1.8 and 2.0 Å, whereas the ground state of AmC has significant occupation of the antibonding orbitals, causing a bond distance of 2.15 Å.

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“…The above described multireference methods and the ANO-RCC basis set were successfully applied in a number of studies on actinide-containing systems. 12,13,[51][52][53][54][55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70] The electronic spectra have been evaluated from the Einstein coefficient values (being directly related to the spectral intensities) computed at the SO-CASPT2 level. 71 The spectra were evaluated utilizing the relative populations of all computed SO states obtained by the Boltzmann equation.…”

Section: +mentioning

confidence: 99%

Theoretical study of the electronic spectra of neutral and cationic NpO and NpO2

Kovács

Infante

2015

The Journal of Chemical Physics

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The electronic of neutral NpO and NpO2 as well as of their mono- (NpO+, NpO2+) and dications (NpO2+, NpO22+) were studied using multiconfigurational relativistic quantum chemical calculations at the complete active space self-consistent field/CASPT2 level of taking into account The active space included 16 orbitals: all the 7s, 6d, and 5f orbitals of together with selected orbitals of oxygen. The vertical on the geometries have been computed up to ca. 35 000 cm−1. The gas-phase electronic were evaluated on the basis of the computed Einstein coefficients at 298 K and 3000 K. The computed vertical transition show good agreement with previous condensed-phase results on NpO2+ and NpO22+.

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Theoretical study of Pu and Am tetracarbide molecules

Cited by 9 publications

References 49 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

Theoretical study of actinide monocarbides (ThC, UC, PuC, and AmC)

Theoretical study of the electronic spectra of neutral and cationic NpO and NpO2

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Theoretical study of Pu and Am tetracarbide molecules

Cited by 9 publications

References 49 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

Theoretical study of actinide monocarbides (ThC, UC, PuC, and AmC)

Theoretical study of the electronic spectra of neutral and cationic NpO and NpO2

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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