Reactions of gas-phase uranyl formate/acetate anions: reduction of carboxylate ligands to aldehydes by intra-complex hydride attack.

In a previous study, electrospray ionization, collision-induced dissociation (CID), and gas-phase ion-molecule reactions were used to create and characterize ions derived from homogeneous precursors composed of a uranyl cation (UVIO22+) coordinated by either formate or acetate ligands [E. Perez, C. Hanley, S. Koehler, J. Pestok, N. Polonsky and M. Van Stipdonk, Gas phase reactions of ions derived from anionic uranyl formate and uranyl acetate complexes, J. Am. Soc. Mass Spectrom., 2016, 27, 1989-1998]. Here, we describe a follow-up study of anionic complexes that contain a mix of formate and acetate ligands, namely [UO2(O2C-CH3)2(O2C-H)]- and [UO2(O2C-CH3)(O2C-H)2]-. Initial CID of either anion causes decarboxylation of a formate ligand to create carboxylate-coordinated U-hydride product ions. Subsequent CID of the hydride species causes elimination of acetaldehyde or formaldehyde, consistent with reactions that include intra-complex hydride attack upon bound acetate or formate ligands, respectively. Density functional theory (DFT) calculations reproduce the experimental observations, including the favored elimination of formaldehyde over acetaldehyde by hydride attack during CID of [UO2(H)(O2C-CH3)(O2C-H)]-. We also discovered that MSn CID of the acetate-formate complexes leads to generation of the oxyl-methide species, [UO2(O)(CH3)]-, which reacts with H2O to generate [UO2(O)(OH)]-. DFT calculations support the observation that formation of [UO2(O)(OH)]- by elimination of CH4 is favored over H2O addition and rearrangement to create [UO2(OH)2(CH3)]-.

Intrinsic reactivity of [OUCH]+ : Apparent synthesis of [OUS]+ by reaction with CS2.

RATIONALE: Building on our report that collision-induced dissociation (CID) can be used to create the highly reactive U-alkylidyne species [O=U≡CH]+ , our goal was to determine whether the species could be as an intermediate for synthesis of [OUS]+ by reaction with carbon disulfide (CS2 ). METHODS: Cationic uranyl-propiolate precursor ions were generated by electrospray ionization, and multiple-stage CID in a linear trap instrument was used to prepare [O=U≡CH]+ . Neutral CS2 was admitted into the trap through a modified He inlet and precision leak valves. RESULTS: The [O=U≡CH]+ ion reacts with CS2 to generate [OUS]+ . CID of [OUS]+ causes elimination of the axial sulfide ligand to generate [OU]+ . Using isotopically labeled reagent, we found that [OUS]+ reacts with O2 to create [UO2 ]+ . CONCLUSIONS: [O=U≡CH]+ proves to be a useful reagent ion for synthesis of [OUS]+ , a species that to date has only been created by gas-phase reactions of U+ and U2+ . Dissociation of [OUS]+ to create [OU]+ , but not [US]+ , and the efficient conversion of the species into [UO2 ]+ , is consistent with the relative differences in U-O and U-S bond energies.

Intrinsic chemistry of [OUCH]+: reactions with H2O, CH3C[triple bond, length as m-dash]N and O2.

We report the first experimental study of the intrinsic chemistry of a U-methylidyne species, focusing on reaction of [OUCH]+ with H2O, O2 and CH3C[triple bond, length as m-dash]N in the gas phase. DFT was also used to determine reaction pathways, and establish the mechanism by which [OUCH]+ is formed through collision-induced dissociation of [UO2(C[triple bond, length as m-dash]CH)]+.

Two-dimensional optical quasicrystal potentials for ultracold atom experiments.

Quasicrystals are nonperiodic structures having no translational symmetry but nonetheless possessing long-range order. The material properties of quasicrystals, particularly their low-temperature behavior, defy easy description. We present a compact optical setup for creating quasicrystal optical potentials with five-fold symmetry using interference of nearly co-propagating beams for use in ultracold atom quantum simulation experiments. We verify the optical design through numerical simulations and demonstrate a prototype system. We also discuss generating phason excitations and quantized transport in the quasicrystal through phase modulation of the beams.

Isotope labeling and infrared multiple-photon photodissociation investigation of product ions generated by dissociation of [ZnNO3(CH3OH)2]+: Conversion of methanol to formaldehyde.

Electrospray ionization was used to generate species such as [ZnNO3(CH3OH)2]+ from Zn(NO3)2•XH2O dissolved in a mixture of CH3OH and H2O. Collision-induced dissociation of [ZnNO3(CH3OH)2]+ causes elimination of CH3OH to form [ZnNO3(CH3OH)]+. Subsequent collision-induced dissociation of [ZnNO3(CH3OH)]+ causes elimination of 47 mass units (u), consistent with ejection of HNO2. The neutral loss shifts to 48 u for collision-induced dissociation of [ZnNO3(CD3OH)]+, demonstrating the ejection of HNO2 involves intra-complex transfer of H from the methyl group methanol ligand. Subsequent collision-induced dissociation causes the elimination of 30 u (32 u for the complex with CD3OH), suggesting the elimination of formaldehyde (CH2 = O). The product ion is [ZnOH]+. Collision-induced dissociation of a precursor complex created using CH3-18OH shows the isotope label is retained in CH2 = O. Density functional theory calculations suggested that the "rearranged" product, ZnOH with bound HNO2 and formaldehyde is significantly lower in energy than ZnNO3 with bound methanol. We therefore used infrared multiple-photon photodissociation spectroscopy to determine the structures of both [ZnNO3(CH3OH)2]+ and [ZnNO3(CH3OH)]+. The infrared spectra clearly show that both ions contain intact nitrate and methanol ligands, which suggests that rearrangement occurs during collision-induced dissociation of [ZnNO3(CH3OH)]+. Based on the density functional theory calculations, we propose that transfer of H, from the methyl group of the CH3OH ligand to nitrate, occurs in concert with the formation of a Zn-C bond. After dissociation to release HNO2, the product rearranges with the insertion of the remaining O atom into the Zn-C bond. Subsequent C-O bond cleavage, with H transfer, produces an ion-molecule complex composed of [ZnOH]+ and O = CH2.

Revealing Disparate Chemistries of Protactinium and Uranium. Synthesis of the Molecular Uranium Tetroxide Anion, UO4.

The synthesis, reactivity, structures, and bonding in gas-phase binary and complex oxide anion molecules of protactinium and uranium have been studied by experiment and theory. The oxalate ions, AnVO2(C2O4)-, where An = Pa or U, are essentially actinyl ions, AnVO2+, coordinated by an oxalate dianion. Both react with water to yield the pentavalent hydroxides, AnVO(OH)2(C2O4)-. The chemistry of Pa and U becomes divergent for reactions that result in oxidation: whereas PaVI is inaccessible, UVI is very stable. The UVO2(C2O4)- complex exhibits a remarkable spontaneous exothermic replacement of the oxalate ligand by O2 to yield UO4- and two CO2 molecules. The structure of the uranium tetroxide anion is computed to correspond to distorted uranyl, UVIO22+, coordinated in the equatorial plane by two equivalent O atoms each having formal charges of -1.5 and U-O bond orders intermediate between single and double. The unreactive nature of PaVO2(C2O4)- toward O2 is a manifestation of the resistance toward oxidation of PaV, and clearly reveals the disparate chemistries of Pa and U. The uranium tetroxide anion, UO4-, reacts with water to yield UO5H2-. Infrared spectra obtained for UO5H2- confirm the computed lowest-energy structure, UO3(OH)2-.

Collision-induced dissociation of uranyl-methoxide and uranyl-ethoxide cations: Formation of UO2 H(+) and uranyl-alkyl product ions.

RATIONALE: The lower levels of adventitious H2 O in a linear ion trap allow the fragmentation reactions of [UO2 OCH3 ](+) and [UO2 OCH2 CH3 ](+) to be examined in detail. METHODS: Methanol- and ethanol-coordinated UO2 (2+) -alkoxide precursors were generated by electrospray ionization (ESI). Multiple-stage tandem mass spectrometry (MS(n) ) and collision-induced dissociation (CID) were performed using a linear ion trap mass spectrometer. RESULTS: CID of [UO2 OCH3 (CH3 OH)n ](+) and [UO2 OCH2 CH3 (CH3 CH2 OH)n ](+) , n = 3 and 2, causes loss of neutral alcohol ligands, leading ultimately to bare uranyl-alkoxide species. Comparison of 'native' to deuterium-labeled precursors reveals dissociation pathways not previously observed in 3-D ion trap experiments. CONCLUSIONS: UO2 H(+) is generated from [UO2 OCH3 ](+) by transfer of H from the methyl group. Variable-energy and variable-time CID experiments suggest that the apparent threshold for production of UO2 H(+) is lower than for UO2 (+) , but the pathway is kinetically less favored for the former than for the latter. CID experiments reveal that [UO2 OCH2 CH3 ](+) dissociates to generate [UO2 CH3 ](+) , a relatively rare species with a U-C bond, and [UO2 (O = CH2 )](+) .

Coherent Addressing of Individual Neutral Atoms in a 3D Optical Lattice.

We demonstrate arbitrary coherent addressing of individual neutral atoms in a 5×5×5 array formed by an optical lattice. Addressing is accomplished using rapidly reconfigurable crossed laser beams to selectively ac Stark shift target atoms, so that only target atoms are resonant with state-changing microwaves. The effect of these targeted single qubit gates on the quantum information stored in nontargeted atoms is smaller than 3×10^{-3} in state fidelity. This is an important step along the path of converting the scalability promise of neutral atoms into reality.

Gas-phase synthesis of [OU-X]+ (X = Cl, Br and I) from a UO22+ precursor using ion-molecule reactions and an [OUCH]+ intermediate.

Difficulty in the preparation of gas-phase ions that include U in middle oxidation states(III,IV) have hampered efforts to investigate intrinsic structure, bonding and reactivity of model species. Our group has used preparative tandem mass spectrometry (PTMS) to synthesize a gas-phase U-methylidyne species, [OUCH]+, by elimination of CO from [UO2(CCH)]+ [M. J. van Stipdonk, I. J. Tatosian, A. C. Iacovino, A. R. Bubas, L. Metzler, M. C. Sherman and A. Somogyi, J. Am. Soc. Mass Spectrom., 2019, 30, 796-805], which has been used as an intermediate to create products such as [OUN]+ and [OUS]+ by ion-molecule reactions. Here, we investigated the reactions of [OUCH]+ with a range of alkyl halides to determine whether the methylidyne is a also a useful intermediate for production and study of the oxy-halide ions [OUX]+, where X = Cl, Br and I, formally U(IV) species for which intrinsic reactivity data is relatively scarce. Our experiments demonstrate that [OUX]+ is the dominant product ion generated by reaction [OUCH]+ with neutral regents such as CH3Cl, CH3CH2Br and CH2CHCH2I.

Conversion of a UO22+ Precursor to UH+ and U+ Using Tandem Mass Spectrometry to Remove Both "yl" Oxo Ligands.

Multiple-stage collision-induced dissociation (CID) of a uranyl propiolate cation, [UO2(O2C-C≡CH)]+, can be used to prepare the U-methylidyne species [O═U≡CH]+ [J. Am. Soc. Mass Spectrom. 2019, 30, 796-805]. Here, we report that CID of [O═U≡CH]+ causes elimination of CO to create [UH]+, followed by a loss of H• to generate U+. A feasible, multiple-step pathway for the generation of [UH]+ was identified using DFT calculations. These results provide the first demonstration that multiple-stage CID can be used to prepare both U+ and UH+ directly from a UO22+ precursor for the subsequent investigation of ion-molecule reactivity.

3D projection sideband cooling.

We demonstrate 3D microwave projection sideband cooling of trapped, neutral atoms. The technique employs state-dependent potentials that enable microwave photons to drive vibration-number reducing transitions. The particular cooling sequence we employ uses minimal spontaneous emission, and works even for relatively weakly bound atoms. We cool 76% of atoms to their 3D vibrational ground states in a site-resolvable 3D optical lattice.