Electron attachment to MoF{sub 6}, ReF{sub 6}, and WF{sub 6}; reaction of MoF{sub 6}{sup -} with ReF{sub 6} and reaction of Ar{sup +} with MoF{sub 6}
- Department of Physics, University of Puerto Rico, Mayaguez, 00681-9016 (Puerto Rico)
Rate constants were measured for electron attachment to MoF{sub 6}, ReF{sub 6}, and WF{sub 6} in 133 Pa of helium gas using a flowing-afterglow Langmuir-probe apparatus. The experiment is a thorny one because the molecules tend to form oxide impurities on feedline surfaces and because of thermal decomposition of MoF{sub 6} on surfaces as the gas temperature is increased. The electron attachment rate constant for MoF{sub 6} is (2.3{+-}0.8)x10{sup -9} cm{sup 3} s{sup -1} at 297 K; only MoF{sub 6}{sup -} is formed in the temperature range of 297-385 K. The rate constant increases with temperature up to the point where decomposition becomes apparent. Electron attachment to ReF{sub 6} occurs with a rate constant of (2.4{+-}0.8)x10{sup -9} cm{sup 3} s{sup -1} at 297 K; only ReF{sub 6}{sup -} is produced. MoF{sub 6}{sup -} reacts with ReF{sub 6} to form ReF{sub 6}{sup -} on essentially every collision, showing definitively that the electron affinity of ReF{sub 6} is greater than that of MoF{sub 6}. A rate constant of (5.0{+-}1.3)x10{sup -10} cm{sup 3} s{sup -1} was measured for this ion-molecule reaction at 304 K. The reverse reaction is not observed. The reaction of Ar{sup +} with MoF{sub 6} was found to produce MoF{sub 5}{sup +}+F, with a rate constant of (1.8{+-}0.5)x10{sup -9} cm{sup 3} s{sup -1}. WF{sub 6} attaches electrons so slowly at room temperature that the attachment rate was below detection level ({<=}10{sup -12} cm{sup 3} s{sup -1}). By 552 K, the attachment rate constant reaches a value of (2{+-}1)x10{sup -10} cm{sup 3} s{sup -1}.
- OSTI ID:
- 20783300
- Journal Information:
- Journal of Chemical Physics, Vol. 124, Issue 22; Other Information: DOI: 10.1063/1.2202851; (c) 2006 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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