Gas-Phase Oxidation of Cm<sup>+</sup> and Cm<sup>2+</sup> − Thermodynamics of Neutral and Ionized CmO

Gibson, John K.; Haire, R.G.; Santos, Marta; Matos, António Pires de; Marçalo, Joaquim

doi:10.1021/jp8047899

Cited by 24 publications

(61 citation statements)

References 48 publications

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“…efficiency for Am + . These reactivity trends have been observed before in several instances, 11,12 specifically in the reactions of An + with oxidants, [55][56][57][58] and correlate with the magnitude of the promotion energies from the ground state to an excitedstate configuration of the An + ion, where two unpaired non-f electrons are available, either 5f nÀ2 6d7s or 5f nÀ2 6d 2 , both of which follow the same trend. 73,74 Pu + and Am + , which have sizeable promotion energies (4100 kJ mol À1 72 ), did not react with CS 2 and were the least reactive with COS. Cm + , which follows Pu + and Am + in the promotion energy trend (48 kJ mol À1 , to 5f 7 6d7s 74 ), was less reactive than the early An + ions with both CS 2 and COS.…”

Section: Resultssupporting

confidence: 78%

“…The experimental approach has been described previously for comparable studies of the An oxides from Th to Cm. [55][56][57][58] A summary of the methods and details specific to the present work are provided here.…”

Section: Methodsmentioning

confidence: 99%

“…The metal-dependent formation of AnS 2 + and AnOS + ions (see previous section also) appears to confirm the high stability of Pa(V) and U(V) species in the gas phase; the accessibility of formally Th(V) species, ThOS + and ThS 2 + , and the lower stability of An(V) species for the transuranics from Np to Cm, are in line with previous observations for the corresponding oxide systems. [55][56][57][58] The thermodynamically more favourable oxidants CH 2 O and NO (see next section) were also used in the case of CmS + . Formation of the monoxide ion was then observed, according to eqn (6) (X = CH 2 , N), with moderate reaction efficiencies (…”

Section: Reactions Of Ans + Ions With Co 2 Cos and Other Oxidantsmentioning

confidence: 99%

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Actinide sulfides in the gas phase: experimental and theoretical studies of the thermochemistry of AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm)

Pereira

Marsden

Marçalo

et al. 2011

Phys. Chem. Chem. Phys.

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The gas-phase thermochemistry of actinide monosulfides, AnS, was investigated experimentally and theoretically. Fourier transform ion cyclotron resonance mass spectrometry was employed to study the reactivity of An(+) and AnO(+) (An = Th, Pa, U, Np, Pu, Am and Cm) with CS(2) and COS, as well as the reactivity of the produced AnS(+) with oxidants (COS, CO(2), CH(2)O and NO). From these experiments, An(+)-S bond dissociation energies could be bracketed. Density functional theory studies of the energetics of neutral and monocationic AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm) provided values for bond dissociation energies and ionization energies; the computed energetics of neutral and monocationic AnO were also obtained for comparison. The theoretical data, together with comparisons with known An(+)-O bond dissociation energies and M(+)-S and M(+)-O dissociation energies for the early transition metals, allowed for the refining of the An(+)-S bond dissociation energy ranges obtained from experiment. Examination of the reactivity of AnS(+) with dienes, coupled to comparisons with reactivities of the AnO(+) analogues, systematic considerations and the theoretical results, allowed for the estimation of the ionization energies of the AnS; the bond dissociation energies of neutral AnS were consequently derived. Estimates for the case of AcS were also made, based on correlations of the data for the other An and the electronic energetics of neutral and ionic An. The nature of the bonding in the elementary molecular actinide chalcogenides (oxides and sulfides) is discussed, based on both the experimental data and the computed electronic structures. DFT calculations of ionization energies for the actinide atoms and the diatomic sulfides and oxides are relatively reliable, but the calculation of bond dissociation energies is not uniformly satisfactory, either with DFT or CCSD(T). A key conclusion from both the experimental and theoretical results is that the 5f electrons do not substantially participate in actinide-sulfur bonding. We emphasize that actinides form strikingly strong bonds with both oxygen and sulfur.

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Section: Resultssupporting

confidence: 78%

Section: Methodsmentioning

confidence: 99%

Section: Reactions Of Ans + Ions With Co 2 Cos and Other Oxidantsmentioning

confidence: 99%

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Actinide sulfides in the gas phase: experimental and theoretical studies of the thermochemistry of AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm)

Pereira

Marsden

Marçalo

et al. 2011

Phys. Chem. Chem. Phys.

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“…We have previously performed several FTICR/MS studies of the reactivity of An 2+ ions, with An from Th to Cm, [17][18][19][20] comprising mostly reactions with a variety of oxidants and also an early investigation of the reactivity of Th 2+ and U 2+ with arenes. 21 Jackson et al have studied the reactivity of U 2+ with oxygen and water using a quadrupole ion trap.…”

Section: Introductionmentioning

confidence: 99%

Gas-phase reactions of doubly charged actinide cations with alkanes and alkenes—probing the chemical activity of 5f electrons from Th to Cm

Marçalo¹,

Santos²,

Gibson

2011

Phys. Chem. Chem. Phys.

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Small alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) were used to probe the gas-phase reactivity of doubly charged actinide cations, An(2+) (An = Th, Pa, U, Np, Pu, Am, Cm), by means of Fourier transform ion cyclotron resonance mass spectrometry. Different combinations of doubly and singly charged ions were observed as reaction products, comprising species formed via metal-ion induced eliminations of small molecules, simple adducts and ions resulting from electron, hydride or methide transfer channels. Th(2+), Pa(2+), U(2+) and Np(2+) preferentially yielded doubly charged products of hydrocarbon activation, while Pu(2+), Am(2+) and Cm(2+) reacted mainly through transfer channels. Cm(2+) was also capable of forming doubly charged products with some of the hydrocarbons whereas Pu(2+) and Am(2+) were not, these latter two ions conversely being the only for which adduct formation was observed. The product distributions and the reaction efficiencies are discussed in relation to the electronic configurations of the metal ions, the energetics of the reactions and similar studies previously performed with doubly charged lanthanide and transition metal cations. The conditions for hydrocarbon activation to occur as related to the accessibility of electronic configurations with one or two 5f and/or 6d unpaired electrons are examined and the possible chemical activity of the 5f electrons in these early actinide ions, particularly Pa(2+), is considered.

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“…Experimentally, using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), [2][3][4] new kinetic and thermochemical data for systems involving Pa, 25 Np, 2,14,26 Pu, 2,14 Am, 2,13 and Cm 27 have been obtained by examining reactions of singly and doubly charged cations with oxidants. John M. Haschke et al studied the reaction kinetics of plutonium with oxygen, water and humid air, 28 and demonstrated the main reaction products.…”

Section: Introductionmentioning

confidence: 99%

Ab initio molecular dynamics study of the interaction of plutonium with oxygen in the gas phase

et al. 2017

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Gas-Phase Oxidation of Cm⁺ and Cm²⁺ − Thermodynamics of Neutral and Ionized CmO

Abstract: Fourier transform ion cyclotron resonance mass spectrometry was employed to study the products and kinetics of gas-phase reactions of Cm + and Cm 2+ ; parallel studies were carried out with La +/2+ , Gd +/2+ and Lu +/2+ . Reactions with oxygen-donor molecules

Cited by 24 publications

References 48 publications

Actinide sulfides in the gas phase: experimental and theoretical studies of the thermochemistry of AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm)

Actinide sulfides in the gas phase: experimental and theoretical studies of the thermochemistry of AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm)

Gas-phase reactions of doubly charged actinide cations with alkanes and alkenes—probing the chemical activity of 5f electrons from Th to Cm

Ab initio molecular dynamics study of the interaction of plutonium with oxygen in the gas phase

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Gas-Phase Oxidation of Cm+ and Cm2+ − Thermodynamics of Neutral and Ionized CmO

Abstract: Fourier transform ion cyclotron resonance mass spectrometry was employed to study the products and kinetics of gas-phase reactions of Cm + and Cm 2+ ; parallel studies were carried out with La +/2+ , Gd +/2+ and Lu +/2+ . Reactions with oxygen-donor molecules

Cited by 24 publications

References 48 publications

Actinide sulfides in the gas phase: experimental and theoretical studies of the thermochemistry of AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm)

Actinide sulfides in the gas phase: experimental and theoretical studies of the thermochemistry of AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm)

Gas-phase reactions of doubly charged actinide cations with alkanes and alkenes—probing the chemical activity of 5f electrons from Th to Cm

Ab initio molecular dynamics study of the interaction of plutonium with oxygen in the gas phase

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Gas-Phase Oxidation of Cm⁺ and Cm²⁺ − Thermodynamics of Neutral and Ionized CmO