Hydrogen bonding in acetone clusters probed by near-edge x-ray absorption fine structure spectroscopy in the carbon and oxygen K-edge regions.
Hydrogen bonding in acetone clusters was investigated using near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and density functional theory calculations in the carbon and oxygen K-edge regions. The partial-ion-yield (PIY) curves of the cluster ions were measured as the NEXAFS spectra of acetone clusters. In the carbon K-edge region, the first resonance peak, which was assigned to the C(CO) 1s-->pi( *)(C=O) resonance transition, showed no substantial change in the PIY curves of the acetone clusters, while the C(CH3) 1s-->3ppi(CH(3)) excitation feature was found to be strongly suppressed. The selective suppression of the C(CH3) 1s-->3ppi(CH(3)) resonance transition can be explained by the change in the character of the 3ppi(CH(3)) orbital due to the C=O...H-C type of hydrogen-bonding interaction. On the other hand, the NEXAFS spectra of the acetone molecule and clusters were almost identical in the oxygen K-edge region, except for a small shift in the pi( *)(C=O) resonance of 0.13 eV, because the character of the pi( *)(C=O) orbital remained, regardless of the C=O...H-C 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
Takahashi
O
O
Yamashita
K
K
Yamaguchi
T
T
Okada
K
K
Tabayashi
K
K
Gejo
T
T
Honma
K
K
D000096:Acetone / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D004583:Electrons; D006860:Hydrogen Bonding; D013058:Mass Spectrometry; D008958:Models, Molecular; D008968:Molecular Conformation; D010100:Oxygen / Q000737:chemistry*; D056928:X-Ray Absorption Spectroscopy
D000096:Acetone; D002244:Carbon; D010100:Oxygen