Hydrogen bonding in methanol clusters probed by inner-shell photoabsorption spectroscopy in the carbon and oxygen K-edge regions

Journal Article · Fri Mar 28 04:00:00 EDT 2008 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2898536· OSTI ID:21104013

Tamenori, Y ^[1]; Okada, K; Takahashi, O; Arakawa, S; Tabayashi, K ^[2]; Hiraya, A ^[3]; Gejo, T; Honma, K ^[4]

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1. Japan Synchrotron Radiation Research Institute/SPring-8, 1-1-1 Kouto, Sayo, Hyogo 679-5198 (Japan)
2. Department of Chemistry, Hiroshima University, Higashi-Hiroshima, Hiroshima 739-8526 (Japan)
3. Department of Physical Science, Hiroshima University, Higashi-Hiroshima, Hiroshima 739-8526 (Japan)
4. Department of Material Science, University of Hyogo, 3-2-1 Kohto, Kamigori, Hyogo 678-1297 (Japan)

Hydrogen bonding in methanol clusters has been investigated by using inner-shell photoabsorption spectroscopy and density functional theory (DFT) calculations in the carbon and oxygen K-edge regions. The partial-ion-yield (PIY) curves of H(CH{sub 3}OH){sub n}{sup +} were measured as the soft x-ray absorption spectra of methanol clusters. The first resonance peak in the PIY curves, which is assigned to the {sigma}*(O-H) resonance transition, exhibits a 1.20 eV blueshift relative to the total-ion-yield (TIY) curves of molecular methanol in the oxygen K-edge region, while it exhibits a shift of only 0.25 eV in the carbon K-edge region. Decreased intensities of the transitions to higher Rydberg orbitals were observed in the PIY curves of the clusters. The drastic change in the {sigma}*(O-H) resonance transition is interpreted by the change in the character of the {sigma}*(O-H) molecular orbital at the H-donating OH site due to the hydrogen-bonding interaction.

• OSTI ID: 21104013
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 12 Vol. 128; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ABSORPTION SPECTRA
ABSORPTION SPECTROSCOPY
CHEMICAL BONDS
DENSITY FUNCTIONAL METHOD
EV RANGE 01-10
IONS
METHANOL
MILLI EV RANGE
RYDBERG STATES
SOFT X RADIATION
X-RAY SPECTRA