Intensity gaps in M+ (CH3OH)n as studied by laser ablation—molecular beam method

Kaya, Takaaki; Horiki, Yasuhiro; Kobayashi, Makoto; Shinohara, Hisanori; Sato, Hiroyasu

doi:10.1016/0009-2614(92)80071-i

Cited by 24 publications

(26 citation statements)

References 14 publications

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“…Sato and co-workers 15 observed the elimination of hydrogen molecules to give fragment complex ions Ti + (CH 2 O)(CH 3 OH) n-1 , in addition to the formation of clustered complex ions Ti + (CH 3 OH) n . An especially interesting question that arises in the reaction of Ti + with methanol is whether the Ti + ion abstracts three hydrogen atoms from the same methanol molecule or from three different methanol molecules within heteroclusters.…”

Section: Resultsmentioning

confidence: 97%

Intracluster Ion−Molecule Reactions of Ti⁺with Methanol Clusters

et al. 2002

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The intracluster ion-molecule reactions occurring within the titanium/methanol heterocluster ions are studied using a simple cluster source based on the mixing of the laser-ablated plasma with the supersonic expansion of a methanol vapor seeded in Ar carrier gas. The product ions are detected using a reflectron time-of-flight mass spectrometer. The mass spectra exhibit a major sequence of cluster ions with the formula Ti + (CH 3 O) 2 (CH 3 -OH) n , which are attributed to the hydrogen elimination reactions (-2H or -H 2 ) of Ti + ion within the heteroclusters. In addition, heterocluster ions of the types Ti + (CH 3 O)(CH 3 OH) n and Ti + (CH 3 O) 3 (CH 3 OH) n also emerge throughout the observed mass spectra, indicating that consecutive H-eliminations by the Ti + ion occur for up to three methanol molecules. The results from isotope-labeling experiments suggest that H-elimination is the reaction path for O-H bond breaking in Ti + -methanol heteroclusters. The observed TiOH + and TiO + ions are interpreted as arising from the insertion of Ti + ions into the C-O bond in CH 3 OH, followed by CH 3 -and CH 4 -elimination, respectively, from the [HO-Ti + -CH 3 ] intermediate. The experiments also show that the chemical reactivity of heterocluster ions is greatly influenced by cluster size and argon stagnation pressure. The reaction energetics and formation mechanisms of the observed heterocluster ions are also discussed.

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Section: Resultsmentioning

confidence: 97%

Intracluster Ion−Molecule Reactions of Ti⁺with Methanol Clusters

et al. 2002

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“…For example, in the intracluster reactions of Mg + (CD 3 OH) n , the intensities of the product ions MgOCD 3 +(CD 3 OH) n-1 at n ) 14 are very strong, and there are almost no Mg + (CD 3 OH) 14 signals. However, at n ) 15, the H-elimination product appears as a shoulder on the left of the stronger Mg + (CD 3 OH) 15 peak.…”

Section: Deuterium Substitution Effectsmentioning

confidence: 99%

“…Sato and co-workers studied the reaction of Mg + with methanol clusters using the "laser ablation-molecular beam" method. 14 Only the molecular addition products, however, were identified. In a flow-tube reaction studied by Castleman et al, successive solvation products were observed without dehydrogenation up to Mg + (CH 3 OH) 6 .…”

Section: Introductionmentioning

confidence: 99%

Reactions of Alkaline Earth Metal Ions with Methanol Clusters

Yang

1998

J. Phys. Chem. A

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The gas phase reactions between singly charged alkaline earth metal ions (Mg + , Ca + , Sr + and Ba + ) and methanol clusters are studied in a pick-up cluster source. In much the same way as for the alkaline earth metal ion-water cluster systems studied by Fuke et al. (J. Am. Chem. Soc. 1995, 117, 747), anomalous product distributions were observed that are characterized by two product switching regions. The first product switching from M + (CH 3 OH) n to MOCH 3 + (CH 3 OH) n-1 occurs for n at around 5. The MOCH 3 + (CH 3 OH) n-1 species switches back to Mg + (CH 3 OH) n for n at around 15 (second switching). The critical sizes for the first and the second switching were found to be affected by the metal and deuterium substitutions. Ab initio calculations on the structures and energetics of the reactants and products were carried out to facilitate the interpretation of the product switching behaviors.

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“…An early study conducted by Uppal et al [7] using an ion cyclotron resonance, ICR, spectrometer showed no reactivity of Mg + ions toward methanol molecules. Kaya et al [8] observed the formation of Mg + (CH 3 OH) n (n = 1–10) in a laser ablation-molecular beam system with a magic number at n = 2. They attributed this magic number to the formation of a first solvation shell of two methanol molecules around the Mg + ion.…”

Section: Introductionmentioning

confidence: 99%

Intracluster Ion Molecule Reactions Following the Generation of Mg+ Within Polar Clusters

Alsharaeh

2011

IJMS

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In this work we investigated the intracluster ion molecule reactions following the generation of Mg+ within the polar clusters (water, methanol, ether and acetonitrile), using time of flight mass spectrometry. In the case of Mg+/water and Mg+/methanol, dehydrogenation reactions are observed after the addition of five molecules. However, no dehydrogenation reactions are observed in the case of Mg+/ether or Mg+/acetonitrile clusters. This confirms the role of the H atom in (O–H) in the dehydrogenation reaction, and rules out any contribution from the H atom in the CH3 group. In addition, the magic numbers in the time of flight (TOF) mass spectra of the Mg+Xn clusters (X = H2O, CH3OH, CH3OCH3 and CH3CN) have been investigated. Finally, the role of ground electronic magnesium ion Mg+(2S1/2), and excited electronic magnesium ion Mg+(2P1/2) in the dehydrogenation reaction were investigated using Ion Mobility Mass spectrometry. The results offer direct evidence confirming the absence of the electronically excited, Mg+(2P1/2).

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Intensity gaps in M+ (CH3OH)n as studied by laser ablation—molecular beam method

Cited by 24 publications

References 14 publications

Intracluster Ion−Molecule Reactions of Ti⁺with Methanol Clusters

Intracluster Ion−Molecule Reactions of Ti⁺with Methanol Clusters

Reactions of Alkaline Earth Metal Ions with Methanol Clusters

Intracluster Ion Molecule Reactions Following the Generation of Mg+ Within Polar Clusters

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Intensity gaps in M+ (CH3OH)n as studied by laser ablation—molecular beam method

Cited by 24 publications

References 14 publications

Intracluster Ion−Molecule Reactions of Ti+with Methanol Clusters

Intracluster Ion−Molecule Reactions of Ti+with Methanol Clusters

Reactions of Alkaline Earth Metal Ions with Methanol Clusters

Intracluster Ion Molecule Reactions Following the Generation of Mg+ Within Polar Clusters

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Product

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Intracluster Ion−Molecule Reactions of Ti⁺with Methanol Clusters

Intracluster Ion−Molecule Reactions of Ti⁺with Methanol Clusters