Hydrogen bonding in methanol clusters probed by inner-shell photoabsorption spectroscopy in the carbon and oxygen K-edge regions.
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(3)OH)(n)(+) 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.
Tamenori
Y
Y
Japan Synchrotron Radiation Research Institute/SPring-8, 1-1-1 Kouto, Sayo, Hyogo 679-5198, Japan. tamenori@spring8.or.jp
Okada
K
K
Takahashi
O
O
Arakawa
S
S
Tabayashi
K
K
Hiraya
A
A
Gejo
T
T
Honma
K
K