화학공학소재연구정보센터
Journal of Chemical Physics, Vol.107, No.19, 8073-8082, 1997
Orientation and tunneling in monolayer methane: CHD3 physisorbed onto NaCl(100)
Polarized infrared spectra of CHD3 adsorbed on NaCl(100) in the temperature range 5 to 33 K are reported. Doublet features are observed in the nu(1) and nu(4) spectral regions. Analysis of the nu(1) doublet reveals one transition dipole perpendicular to the surface and another transition dipole at 70 +/- 15 degrees from the surface normal. These features are assigned to the C-H stretching vibrations of molecules oriented in a tripod conformation with the hydrogen in the ''top'' position (H-up) and in a tripod with the hydrogen in one of the ''base'' positions (H-down), respectively. The fraction of H-up orientational isomers increases with decreasing temperature. It is shown that an energy splitting between H-up and H-down orientational isomers of 6.9 +/- 0.5 cm(-1) can explain the temperature dependence. Several possible explanations of the energy splitting are explored. Tunneling between orientational isomers is shown to be the only mechanism of reorientation consistent with the observed conversion time scale. (C) 1997 American Institute of Physics.