Structures and vibrational spectroscopy of partially reduced gas-phase cerium oxide clusters

Burow, Asbjoern Manfred; Wende, Torsten; Sierka, Marek; Włodarczyk, Radosław; Sauer, Joachim; Claes, Pieterjan; Jiang, Ling; Meijer, Gerard; Lievens, Peter; Asmis, Knut R.

doi:10.1039/c1cp22129a

Cited by 52 publications

(90 citation statements)

References 73 publications

(127 reference statements)

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“…CenO2n + species are considered to hold an oxygen-centered radical, 6,16,17 whereas CenO2n−1 + have one unpaired electron located in Ce 4f orbitals. 18 For CenO2n+1 + and CenO2n+2 + , the spin distribution remains 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 side-on bound with the Ce center in the most stable structure. 19 Thus, the number ratio of cerium atoms and oxygen atoms in a stable cluster is 1:2, indicating that the cerium atom and the oxygen atom adopt the +4 and −2 charge states, respectively.…”

Section: Stable Cerium Oxide Clustersmentioning

confidence: 93%

Stable Stoichiometry of Gas-Phase Cerium Oxide Cluster Ions and Their Reactions with CO

2015

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Cerium oxide cluster ions, Ce(n)O(2n+x)(+) (n = 2-9, x = -1 to +2), were prepared in the gas phase by laser ablation of a cerium oxide rod in the presence of oxygen diluted in He as the carrier gas. The stable stoichiometry of the cluster ions was investigated using a mass spectrometer in combination with a newly developed post heating device. The oxygen-rich clusters, Ce(n)O(2n+x)(+) (x = 1, 2), were found to release oxygen molecules, and Ce(n)O(2n+x)(+) (x = -1, 0) were exclusively formed by post heating treatment at 573 K. The Ce(n)O(2n-1)(+) and Ce(n)O(2n)(+) clusters were found to be thermally stable, and the oxygen-rich clusters consisted of robust Ce(n)O(2n-1)(+) and Ce(n)O(2n)(+) and weakly bound oxygen atoms. Evaluation of the reactivity of Ce(n)O(2n+x)(+) with CO molecules demonstrated that Ce(n)O(2n)(+) oxidized CO to form Ce(n)O(2n-1)(+) and CO2, and the rate constants of the reaction were in the range of 10(-12)-10(-16) cm(3) s(-1). The CO oxidation reaction was distinct for n = 5, which occurred in parallel with the CO attachment reaction.

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Section: Stable Cerium Oxide Clustersmentioning

confidence: 93%

Stable Stoichiometry of Gas-Phase Cerium Oxide Cluster Ions and Their Reactions with CO

2015

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“…Genetic algorithm Main-group elements and coinage metals Li, [117] Cs, [119] B, [118] Al, [138] Ga, [139] Si, [140] Sn, [130,[134][135][136] Pb, [141] P, [142] As, [142] Bi, [143] Cu, [126,144] Ag, [94,125,126] Au [94,125,126,145] Nanoalloys Na-Si, [127] Sn-Bi, [146,147] Ag-Cu, [126] Au-Cu, [126] Au-Ag [94,125] Oxide a and other systems Li-O, [148] Be-O, [149] Mg-O, [150,151] B-O, [152] Al-O, [153] Ce-O, [154] W-O, [155] Li-F, [156] Al-H, [157] B-C, [158] Li-Al-B, [159] H 2 O-H [160] Complex systems Ag-Lig, [161] Au-Surf, [131,162] Au-Pd-Surf [162] Basin hopping Homoatomic B, <...>…”

Section: Methods System Type Clustersmentioning

confidence: 99%

Global optimization of clusters using electronic structure methods

Heiles

Johnston

2013

Int J of Quantum Chemistry

196

190

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Over the past decade, there has been a significant growth in the development and application of methods for performing global optimization (GO) of cluster and nanoparticle structures using first-principles electronic structure methods coupled to sophisticated search algorithms. This has in part been driven by the desire to avoid the use of empirical potentials (EPs), especially in cases where no reliable potentials exist to guide the search toward reasonable regions of configuration space. This has been facilitated by improvements in the reliability of the search algorithms, increased efficiency of the electronic structure methods, and the development of faster, multiprocessor high-performance computing architectures. In this review, we give a brief overview of GO algorithms, though concentrating mainly on genetic algorithm and basin hopping techniques, first in combination with EPs. The major part of the review then deals with details of the implementation and application of these search methods to allow exploration for global minimum cluster structures directly using electronic structure methods and, in particular, density functional theory. Example applications are presented, ranging from isolated monometallic and bimetallic clusters to molecular clusters and ligated and surface supported metal clusters. Finally, some possible future developments are highlighted.

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“…Additional IR bands may be observed as a result of symmetry lowering and lifting of degeneracies or of IR‐active combination bands involving the ion‐messenger degrees of freedom . In more severe cases, tagging leads to more substantial structural changes in the core ion or/and an energetic reordering of isomers . Kinetic trapping of isomers upon tagging is also possible .…”

Section: Cryogenic Ion Trap Vibrational Spectroscopymentioning

confidence: 99%

“…[79] In more severe cases, tagging leads to more substantial structural changes in the core ion or/and an energetic reordering of isomers. [80][81][82][83][84] Kinetic trappingo fi somers upon tagging is also possible. [78] Helium is typically the messenger of choice, as it represents the weakestp erturber due to its comparably smallp olarizability.A nion-He complexes are considerably more difficult to form and H 2 /D 2 is typically used as am essengerf or negative ions.…”

Section: Cryogenic Ion Trap Vibrational Spectroscopymentioning

confidence: 99%

Identification of Active Sites and Structural Characterization of Reactive Ionic Intermediates by Cryogenic Ion Trap Vibrational Spectroscopy

Schwarz

Asmis

2019

Chemistry A European J

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Cryogenic ion trap vibrational spectroscopy paired with quantum chemistry currently represents the most generally applicable approach for the structural investigation of gaseous cluster ions that are not amenable to direct absorption spectroscopy. Here, we give an overview of the most popular variants of infrared action spectroscopy and describe the advantages of using cryogenic ion traps in combination with messenger tagging and vibrational predissociation spectroscopy. We then highlight a few recent studies that apply this technique to identify highly reactive ionic intermediates and to characterize their reactive sites. We conclude by commenting on future challenges and potential developments in the field.

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Structures and vibrational spectroscopy of partially reduced gas-phase cerium oxide clusters

Cited by 52 publications

References 73 publications

Stable Stoichiometry of Gas-Phase Cerium Oxide Cluster Ions and Their Reactions with CO

Stable Stoichiometry of Gas-Phase Cerium Oxide Cluster Ions and Their Reactions with CO

Global optimization of clusters using electronic structure methods

Identification of Active Sites and Structural Characterization of Reactive Ionic Intermediates by Cryogenic Ion Trap Vibrational Spectroscopy

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