Laser Ablation Mass Spectrometry of Actinide Dioxides: ThO2, UO2, NpO2, PuO2 and AmO2

Gibson, John K.

doi:10.1524/ract.1998.81.2.83

Cited by 10 publications

(9 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The correlation between D°[LnO] and D°[LnO + ] has been discussed by Chandrasekharaiah and Gingerich 27 and suggests that IE(Ln) ≈ IE(LnO) for most Ln and that ionization of most LnO proceeds by removal of an essentially nonbonding electron localized at the metal center. Previous results for ablated AnO + abundances 25…”

Section: Resultsmentioning

confidence: 91%

“…Prior to carrying out the ion−molecule reactions, ablation of the target was examined under vacuum; a positive ion mass spectrum is shown in Figure . Ablation of AnO 2 has been shown to result in AnO + abundances that reflect the An−O dissociation energies, D °[AnO]. , Thus, Am + is dominant and only a minuscule amount of AmO + ( D °[AmO] ≈ 550 kJ mol -1 ) is ablated from AmO 2 (s), whereas copious NpO + ( D °[NpO] = 740 kJ mol -1 ) is ablated from NpO 2 (s). The correlation between D °[LnO] and D °[LnO + ] has been discussed by Chandrasekharaiah and Gingerich and suggests that IE(Ln) ≈ IE(LnO) for most Ln and that ionization of most LnO proceeds by removal of an essentially nonbonding electron localized at the metal center.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Gas-Phase Chemistry of Curium: Reactions of Cm⁺ and CmO⁺ with Alkenes, Acetonitrile, and Hexafluoropropene

Gibson

Haire

1998

J. Phys. Chem. A

Self Cite

View full text Add to dashboard Cite

The metal ions, Cm+, U+, and Tb+, and their oxides, MO+, were reacted in the gas phase with alkenes, acetonitrile, and hexafluoropropene. Product compositions and abundances provide a survey of essential aspects of the gas-phase chemistry of the curium cation, now the heaviest element for which such systematic studies have been carried out (U and Tb were included to provide comparisons). Of particular interest is the difference in behavior between the 4f lanthanide and 5f actinide series and variations in chemistry across the actinide series. The primary emphasis was on reactions with alkenes, particularly dehydrogenation, as indicative of the ability of a M+ to activate C−H bonds (the extent of C−C activation was generally in parallel with that of C−H activation). With acetonitrile and all of the alkenes (except ethene), the three M+ ions induced dehydrogenation. Variations were evident for the different reactant substrates, but the overall qualitative ordering of dehydrogenation efficiency was U+ > Tb+ > Cm+. This order is consistent with the variation in electronic promotion energies (PE) required to provide two spin-unpaired, non-f valence electrons at the M+, i.e., a [Rg]f n -2ds1 configuration (“Rg” = Xe for the lanthanides and Rn for the actinides), to enable its insertion into a C−H bond. The reduced reactivity of Cm+ relative to U+ and Tb+ suggests that the closed-shell 7s electrons of ground Cm+ (8S [Rn]5f7s2) are ineffective in enabling C−H activation and that promotion to the 10D [Rn]5f76d17s1 configuration is prerequisite. The PE[Cm+] (48 kJ mol-1) is only slightly greater than PE[Tb+] (39 kJ mol-1) and the significantly greater reactivity of Tb+ vs Cm+ may reflect that the transition to the prepared “divalent” state (d1s1) is parity forbidden for Cm+. The three MO+ were substantially less reactive than the naked M+ but were comparably reactive to one another, consistent with a multicentered activation process, which is less efficient than direct cleavage of a C−H bond by M+ insertion. With hexafluoropropene, the primary reaction channel was F abstraction and the discrepant reactivities reflected the propensity for U to oxidize to higher valence states compared to Cm or Tb. The terminal MF n + were CmIIIF2 +, TbIIIF2 +, and UIVF4 +, and among the MO+, only UO+ induced F abstraction, producing UOF n + with n = 1−3.

show abstract

Section: Resultsmentioning

confidence: 91%

Section: Resultsmentioning

confidence: 99%

Gas-Phase Chemistry of Curium: Reactions of Cm⁺ and CmO⁺ with Alkenes, Acetonitrile, and Hexafluoropropene

Gibson

Haire

1998

J. Phys. Chem. A

Self Cite

View full text Add to dashboard Cite

show abstract

“…The more reactive M C , particularly U C and Np C , were largely depleted in the presence of a reactant. Thus, whereas vacuum ablation resulted in approximately comparable yields of Np C and NpO 2 C ; 40 the amount of Np C remaining after exposure to propanol was minor (Table 1). …”

Section: Resultsmentioning

confidence: 98%

“…The absence of detectable US 2 C can be attributed to the dearth of ablated U C . 40 In contrast, abundant PuO C was ablated and the lack of PuOS C presumably reflects that PuO C is relatively ineffective at abstracting a sulfur-atom from propanethiol. Presuming the pentavalent bonding structure, O An C S, the evidently decreased stability of PuOS C vs NpOS C is consistent with the general decrease in the stabilities of higher oxidation states upon proceeding across this region of the actinide series.…”

Section: Thiolsmentioning

confidence: 99%

Gas-phase transuranium chemistry: reactions of actinide ions with alcohols and thiols

Gibson¹

1999

J. Mass Spectrom.

Self Cite

View full text Add to dashboard Cite

“…One of the main goals of these studies has been to develop laser ablation methods and laser induced plasma spectroscopy as a tool for elemental analysis. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] An important application of such studies in which laser ablation based analytical techniques have been used is nuclear forensic investigations. 18,19 Laser ablation based mass spectrometry techniques are among the chief analytical approaches used in nuclear forensic investigations because they can provide highly accurate elemental and isotopic information while requiring less mass compared to alternative analytical methods available for such studies.…”

Section: Introductionmentioning

confidence: 99%

Time of flight mass spectrometry with direct extraction of a uranium plasma

Thompson

Alavi

Walensky

et al. 2019

International Journal of Mass Spectrometry

View full text Add to dashboard Cite

We demonstrate a Wiley-McClaren Time of Flight Mass Spectrometer modified to allow direct extraction of ions from a laser-induced plasma. Unlike many other methods that utilize mass spectrometry to investigate laser-induced plasmas, no collisional cooling or further ionization of the plasma is required prior to acceleration, allowing measurements of the plasma ion composition to be obtained directly. Furthermore, we show using the laser ablation of gadolinium as an example that we are able to obtain the translational energy distribution of the plasma directly and infer information about the relative composition of ions within different regions of the plasma plume. The approach is then applied to laser ablation of a uranium sample as a step toward probing the chemistry under conditions relevant to a nuclear fireball for nuclear forensics applications.

show abstract

Laser Ablation Mass Spectrometry of Actinide Dioxides: ThO₂, UO₂, NpO₂, PuO₂ and AmO₂

Cited by 10 publications

References 12 publications

Gas-Phase Chemistry of Curium: Reactions of Cm⁺ and CmO⁺ with Alkenes, Acetonitrile, and Hexafluoropropene

Gas-Phase Chemistry of Curium: Reactions of Cm⁺ and CmO⁺ with Alkenes, Acetonitrile, and Hexafluoropropene

Gas-phase transuranium chemistry: reactions of actinide ions with alcohols and thiols

Time of flight mass spectrometry with direct extraction of a uranium plasma

Contact Info

Product

Resources

About

Laser Ablation Mass Spectrometry of Actinide Dioxides: ThO2, UO2, NpO2, PuO2 and AmO2

Cited by 10 publications

References 12 publications

Gas-Phase Chemistry of Curium: Reactions of Cm+ and CmO+ with Alkenes, Acetonitrile, and Hexafluoropropene

Gas-Phase Chemistry of Curium: Reactions of Cm+ and CmO+ with Alkenes, Acetonitrile, and Hexafluoropropene

Gas-phase transuranium chemistry: reactions of actinide ions with alcohols and thiols

Time of flight mass spectrometry with direct extraction of a uranium plasma

Contact Info

Product

Resources

About

Laser Ablation Mass Spectrometry of Actinide Dioxides: ThO₂, UO₂, NpO₂, PuO₂ and AmO₂

Gas-Phase Chemistry of Curium: Reactions of Cm⁺ and CmO⁺ with Alkenes, Acetonitrile, and Hexafluoropropene

Gas-Phase Chemistry of Curium: Reactions of Cm⁺ and CmO⁺ with Alkenes, Acetonitrile, and Hexafluoropropene