Gas Phase Structure of Micro-Hydrated [Mn(ClO4)]+ and [Mn2(ClO4)3]+ Ions Probed by Infrared Spectroscopy

Rajeev K. Sinha, Edith Nicol, Vincent Steinmetz, Philippe Matre

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

Gas-phase infrared photodissociation spectroscopy is reported for the microsolvated [Mn(ClO4)(H2O)n]+ and [Mn2(ClO4)3(H2O)n]+ complexes from n = 2 to 5. Electrosprayed ions are isolated in an ion-trap where they are photodissociated. The 26003800 cm1 spectral region associated with the OH stretching mode is scanned with a relatively low-power infrared table-top laser, which is used in combination with a CO2 laser to enhance the photofragmentation yield of these strongly bound ions. Hydrogen bonding is evidenced by a relatively broad band red-shifted from the free OH region. Band assignment based on quantum chemical calculations suggest that there is formation of waterperchlorate hydrogen bond within the first coordination shell of high-spin Mn(II). Although the observed spectral features are also compatible with the formation of structures with double-acceptor water in the second shell, these structures are found relatively high in energy compared with structures with all water directly bound to manganese. Using the highly intense IR beam of the free electron laser CLIO in the 8001700 cm1, we were also able to characterize the coordination mode (η2) of perchlorate for two clusters. The comparison of experimental and calculated spectra suggests that the perchlorate ClO stretches are unexpectedly underestimated at the B3LYP level, while they are correctly described at the MP2 level allowing for spectral assignment.

Original languageEnglish
Pages (from-to)758-772
Number of pages15
JournalJournal of the American Society for Mass Spectrometry
Volume21
Issue number5
DOIs
Publication statusPublished - 01-05-2010

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Phase structure
Infrared spectroscopy
Spectrum Analysis
Gases
Ions
Hydrogen bonds
Lasers
Infrared radiation
Photodissociation
Gas Lasers
Water
Free electron lasers
Hydrogen Bonding
Manganese
Stretching
Hydrogen
Spectroscopy
Electrons
perchlorate

All Science Journal Classification (ASJC) codes

  • Structural Biology
  • Spectroscopy

Cite this

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abstract = "Gas-phase infrared photodissociation spectroscopy is reported for the microsolvated [Mn(ClO4)(H2O)n]+ and [Mn2(ClO4)3(H2O)n]+ complexes from n = 2 to 5. Electrosprayed ions are isolated in an ion-trap where they are photodissociated. The 26003800 cm1 spectral region associated with the OH stretching mode is scanned with a relatively low-power infrared table-top laser, which is used in combination with a CO2 laser to enhance the photofragmentation yield of these strongly bound ions. Hydrogen bonding is evidenced by a relatively broad band red-shifted from the free OH region. Band assignment based on quantum chemical calculations suggest that there is formation of waterperchlorate hydrogen bond within the first coordination shell of high-spin Mn(II). Although the observed spectral features are also compatible with the formation of structures with double-acceptor water in the second shell, these structures are found relatively high in energy compared with structures with all water directly bound to manganese. Using the highly intense IR beam of the free electron laser CLIO in the 8001700 cm1, we were also able to characterize the coordination mode (η2) of perchlorate for two clusters. The comparison of experimental and calculated spectra suggests that the perchlorate ClO stretches are unexpectedly underestimated at the B3LYP level, while they are correctly described at the MP2 level allowing for spectral assignment.",
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Gas Phase Structure of Micro-Hydrated [Mn(ClO4)]+ and [Mn2(ClO4)3]+ Ions Probed by Infrared Spectroscopy. / Sinha, Rajeev K.; Nicol, Edith; Steinmetz, Vincent; Matre, Philippe.

In: Journal of the American Society for Mass Spectrometry, Vol. 21, No. 5, 01.05.2010, p. 758-772.

Research output: Contribution to journalArticle

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