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New temperature effect on tunneling reaction in hydrogen, alkane, and ethanol in the solid phase |
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| Authors: | Tetsuo Miyazaki Takayuki Kumada Kenji Komaguchi Yasuyuki Aratono |
| Institution: | a Department of Applied Chemistry, School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-01, Japan b Advanced Science Research Center, Japan Atomic Energy Research Institute, Tokai-mura, Ibaraki 319-11, Japan c Faculty of Engineering, Hiroshima University, Higashi Hiroshima, 739, Japan |
| Abstract: | Rate constants for the tunneling reaction (HD + D → h + D2) in solid HD increase steeply with increasing temperature above 5 K, while they are almost constant below 4.2 K. The apparent activation energy for the tunneling reaction above 5 K is 95 K, which is consistent with the energy (91–112 K) for vacancy formation in solid hydrogen. The results above 5 K were explained by the model that the tunneling reaction was accelerated by a local motion of hydrogen molecules and hydrogen atoms. The model of the tunneling reaction assisted by the local motion of the reactans and products was applied to the temperature dependence of the proton-transfer tunneling reaction (C6H6? + C2H5OH → C6H7 + C2H5O?) in solid ethanol, the tunneling elimination of H2 molecule of H2 molecule ((CH3)2 CHCH(CH3)2+ → (CH3)2 C = C(CH3)2+ + H2) in solid 2,3-dimethylbutane, and the selective tunneling reaction of H atoms in solid neo-C5H12-alkane mixtures. |
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