Identification of Valence Electronic States Reflecting the Hydrogen Bonding in Liquid Ethanol.

The temperature-dependent X-ray emission spectra of liquid ethanol were calculated theoretically using a semi-classical approximation to the Kramers-Heisenberg formula, which includes the dynamical effects induced by a core-hole. Soft X-ray emission spectroscopic measurements were performed to discern the changes in the hydrogen bonding (h-bonding) structure of liquid ethanol using a temperature-controlled liquid cell at 241 and 313 K. The relative intensities of the peaks at approximately 526.5 and 527.1 eV varied with temperature, and the corresponding behavior was reproduced theoretically, although the variation with temperature in the calculated spectra were more enhanced than that in the experiment. The two peaks can be attributed to the 3a″ + 10a' mixed state and pure 3a″ state, respectively, depending on the behavior of the local h-bonding structure. The splitting of the 3a″ component occurred because of the h-bonding behavior of liquid ethanol. Furthermore, the size of the ethanol cluster decreased with an increase in temperature, mainly due to the breaking of the one-donor/one-acceptor type h-bonding. Our studies suggest that the electronic state of liquid ethanol reflects several types of h-bonding structures, and the ratios of these h-bonding types vary with temperature.