Electronic Spectra of Pure Uranyl(V) Complexes:  Characteristic Absorption Bands Due to a UVO2+ Core in Visible and Near-Infrared Regions1

Mizuoka, Koichiro; Tsushima, Satoru; Hasegawa, Miki; Hoshi, Toshihiko; Ikeda, Yasuhisa

doi:10.1021/ic0503838

Cited by 79 publications

(91 citation statements)

References 37 publications

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“…These transitions have been assigned previously by Mizuoka et al 60 as 5f → 5f type. Our calculation suggests that these three peaks are related to 5f → 6d and 5f → 7s transitions.…”

Section: B Orbital Composition Of Uranyl and The Uo 2 + Excitation Esupporting

confidence: 58%

A Fock space coupled cluster study on the electronic structure of the UO2, UO2+, U4+, and U5+ species

Infante

Eliav

Vilkas

et al. 2007

The Journal of Chemical Physics

137

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The ground and excited states of the UO 2 molecule have been studied using a Dirac-Coulomb intermediate Hamiltonian Fock-space coupled cluster approach ͑DC-IHFSCC͒. This method is unique in describing dynamic and nondynamic correlation energies at relatively low computational cost. Spin-orbit coupling effects have been fully included by utilizing the four-component Dirac-Coulomb Hamiltonian from the outset. Complementary calculations on the ionized systems UO 2 + and UO 2 2+ as well as on the ions U 4+ and U 5+ were performed to assess the accuracy of this method. The latter calculations improve upon previously published theoretical work. Our calculations confirm the assignment of the ground state of the UO 2 molecule as a 3 ⌽ 2u state that arises from the 5f 1 7s 1 configuration. The first state from the 5f 2 configuration is found above 10 000 cm −1 , whereas the first state from the 5f 1 6d 1 configuration is found at 5 047 cm −1 .

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“…These transitions have been assigned previously by Mizuoka et al 60 as 5f → 5f type. Our calculation suggests that these three peaks are related to 5f → 6d and 5f → 7s transitions.…”

Section: B Orbital Composition Of Uranyl and The Uo 2 + Excitation Esupporting

confidence: 58%

A Fock space coupled cluster study on the electronic structure of the UO2, UO2+, U4+, and U5+ species

Infante

Eliav

Vilkas

et al. 2007

The Journal of Chemical Physics

137

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“…For example, in nature, the most abundant uranium compound is U 3 O 8 , which can be considered as consisting of one molecule of UO 2 (U IV oxide) and two molecules of UO 3 (U VI oxide). In the laboratory, the most common uranium compounds are the salts of uranyl (UO 2 2ϩ -U VI -containing cation), e.g., UO 2 (NO 3 ) 2 , UO 2 (CH 3 COO) 2 . Uranium compounds with this element at other oxidation states (other than IV and VI) are also known, however, they are less stable, e.g., the U V species in solutions easily undergo disproportionation reaction to U(IV) and U(VI) [2].…”

mentioning

confidence: 99%

Unusual ion UO₄⁻ formed upon collision induced dissociation of [UO₂(NO₃)₃]⁻, [UO₂(ClO₄)₃]⁻, [UO₂(CH₃COO)₃]⁻ ions

Sokalska

Prussakowska

Hoffmann

et al. 2010

J. Am. Soc. Mass Spectrom.

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The following ions [UO 2 (NO 3 Ϫ were generated from respective salts (UO 2 (NO 3 ) 2 , UO 2 (ClO 4 ) 3 , UO 2 (CH 3 COO) 2 ) by laser desorption/ionization (LDI). Collision induced dissociation of the ions has led, among others, to the formation of UO 4 Ϫ ion (m/z 302). The undertaken quantum mechanical calculations showed this ion is most likely to possess square planar geometry as suggested by MP2 results or strongly deformed geometry in between tetrahedral and square planar as indicated by DFT results. Interestingly, geometrical parameters and analysis of electron density suggest it is an U VI compound, in which oxygen atoms bear unpaired electron and negative charge. In the laboratory, the most common uranium compounds are the salts of uranyl (UO 2 2ϩ -U VI -containing cation), e.g., UO 2 (NO 3 ) 2 , UO 2 (CH 3 COO) 2 . Uranium compounds with this element at other oxidation states (other than IV and VI) are also known, however, they are less stable, e.g., the U V species in solutions easily undergo disproportionation reaction to U(IV) and U(VI) [2]. In nature, there are also uranyl peroxides UO 2 (O 2 ), but the respective minerals UO 2 (O 2 )(H 2 O) 2 and UO 2 (O 2 )(H 2 O) 4 do not exist in high abundances [3]. A number of more developed uranyl peroxides were obtained in labs [4 -7].Mass spectrometric studies of uranyl salts (mainly UO 2 (NO 3 ) 2 ) have been reported, first by using FAB (fast atom bombardment) as ionization method [8], and then by electrospray ionization [9 -15]. Most of the studies were performed in the positive ion mode; only Pasilis et al. have performed the ESI analysis in both positive and negative ion modes [10]. In this very excellent paper, the authors have systematically investigated the gasphase uranyl-containing ions and they have examined ligand association/exchange and H/D exchange reactions of the species, using FT-ICR mass spectrometry to obtain accurate mass measurements. In this communication, the collision induced dissociation (CID) of the ions [UO 2 (NOϪ is discussed. The ions were generated from respective salts (UO 2 (NO 3 ) 2 , UO 2 (ClO 4 ) 3 , UO 2 (CH 3 COO) 2 ) by laser desorption/ionization (LDI). As described further, the unusual formation of ion UO 4 Ϫ was detected upon decomposition of the ions subjected to CID. ExperimentalThe LDI mass spectra and LDI MS/MS spectra were obtained on a Waters/Micromass (Manchester, UK) Q-TOF Premier mass spectrometer (software MassLynx ver. 4.1; Manchester, UK) fitted with a 200 Hz repetition rate Nd/YAG laser ( ϭ 355 nm, power density 10 7 W/cm 2 ). For MS/MS experiments, argon was used as a collision gas at the flow-rate 0.5 mL/min in the collision cell. Collision energy (CE -the most important parameter for MS/MS experiments) is indicated in each MS/MS spectrum presented further.To prepare the target spots, 1 L of methanol solution containing uranyl salts was used (the concentration was of about 0.1 mol/dm [3]. After a few min at room temperature, the spot was dry and LDI mass spectra could be recorded. If the concentra...

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“…During the last decade an increasing interest in complex formation of uranyl(V) could be observed. [14][15][16][17][18][19][20][21] According to the resulting conclusions, both UO 2 2+ and UO 2 + can often be coordinated by the same type of ligand but in the latter case stability constants are lower. Therefore such a possibility should be taken into account when voltammetric data from uranyl(VI)-selenate system are treated.…”

Section: Resultsmentioning

confidence: 91%

Voltammetric Study of Uranyl–Selenium Interactions. Part 2. Uranyl(V) Selenate Complex

2013

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Abstract. Under the influence of recently published papers and some older own results, complex formation in uranyl(VI)-selenium(VI) system was reinvestigated at the ionic strengths of 0.1 and 3.0 mol L -1 . Using electrolyzed selenate solutions (and square-wave voltammetry as a measuring technique) two coordination species at the higher electrolyte concentration (log β 1 = 1.48 ± 0.01, log β 2 = 2.4 ± 0.1) were recognized, in agreement with the literature data based on other experimental methods. For successful interpretation of the voltammetric data, previously unknown weak complex (log β 01 =0.7 ± 0.1) of the reduction product, i.e. uranyl(V) should also be included in the model. At the lower electrolyte concentration (0.1 mol L -1 ), formation of complexes other than UO 2 SeO 4 0 cannot be unambiguously confirmed due to the narrow ligand concentration range.Concerning the number of coordination species and their stability constants, seemingly different results that arise from voltammetry and other (independent) experimental methods reflect the fact that the former, in addition to the complexation of initially present metal ion, "sees" the coordination of its reduction product with the ligand of interest, too. When both processes are taken into account during treatment of voltammetric data, such differences disappear. (doi: 10.5562/cca1952)

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Electronic Spectra of Pure Uranyl(V) Complexes: Characteristic Absorption Bands Due to a U^VO₂⁺ Core in Visible and Near-Infrared Regions¹

Cited by 79 publications

References 37 publications

A Fock space coupled cluster study on the electronic structure of the UO2, UO2+, U4+, and U5+ species

A Fock space coupled cluster study on the electronic structure of the UO2, UO2+, U4+, and U5+ species

Unusual ion UO₄⁻ formed upon collision induced dissociation of [UO₂(NO₃)₃]⁻, [UO₂(ClO₄)₃]⁻, [UO₂(CH₃COO)₃]⁻ ions

Voltammetric Study of Uranyl–Selenium Interactions. Part 2. Uranyl(V) Selenate Complex

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Electronic Spectra of Pure Uranyl(V) Complexes: Characteristic Absorption Bands Due to a UVO2+ Core in Visible and Near-Infrared Regions1

Cited by 79 publications

References 37 publications

A Fock space coupled cluster study on the electronic structure of the UO2, UO2+, U4+, and U5+ species

A Fock space coupled cluster study on the electronic structure of the UO2, UO2+, U4+, and U5+ species

Unusual ion UO4− formed upon collision induced dissociation of [UO2(NO3)3]−, [UO2(ClO4)3]−, [UO2(CH3COO)3]− ions

Voltammetric Study of Uranyl–Selenium Interactions. Part 2. Uranyl(V) Selenate Complex

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Electronic Spectra of Pure Uranyl(V) Complexes: Characteristic Absorption Bands Due to a U^VO₂⁺ Core in Visible and Near-Infrared Regions¹

Unusual ion UO₄⁻ formed upon collision induced dissociation of [UO₂(NO₃)₃]⁻, [UO₂(ClO₄)₃]⁻, [UO₂(CH₃COO)₃]⁻ ions