Far-ultraviolet (FUV) spectroscopy holds great potential in revealing electronic transitions and structure of a wide range of molecules in condensed phases. FUV spectroscopy in the 145-200 nm regions has recently been a matter of intense interest because many kinds of organic and inorganic materials in the condensed phase show bands coming from electronic transitions in the FUV region. Since the molar absorption coefficient is very high (~105 mol-1 dm3 cm-1) in the FUV region, the electronic states and structure mainly for gas molecules has been investigated for a long time. On the other hand, as to molecules in the condensed phase transmittance spectra could not measure because of high molecular density, and reflection spectroscopy has been used to observe spectra of solid samples in the FUV region. Accordingly, electronic spectroscopy for molecules of sigma orbital has been a relatively undeveloped research area. To solve the above difficulties of FUV spectroscopy we have recently developed a totally new UV spectrometer based on attenuated total reflection (ATR) that enables us to measure spectra of liquid and solid samples in the 140–300 nm region. Liquid n- and branched alkanes were studied using ATR-FUV. FUV spectra of these molecules can be explained by quantum chemical calculation and almost similar to those in the gas phase. However, FUV spectra of solid alkanes show drastic alternations from those in the liquid phase. Changes in the orbital of alkanes in the solid phase were related to abnormal phase behavior of these molecules
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