Photodetachment imaging studies of the electron affinity of CF3

被引:59
作者
Deyerl, HJ [1 ]
Alconcel, LS [1 ]
Continetti, RE [1 ]
机构
[1] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA
关键词
D O I
10.1021/jp003137k
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The photoelectron spectra of the trifluoromethyl anion, CF3-, at 355 and 258 nm are reported, Simulation of the partially resolved vibrational structure is used to extract the adiabatic electron affinity, AEA[CF3] = 1.82 +/- 0.05 eV. The heat of formation for the trifluoromethyl anion derived from the adiabatic electron affinity (DeltaH(f.298)(0)[CF3-] = -153.4 +/- 1.5 kcal/mol) is compared to the high-accuracy "isodesmic bond additivity corrected" (BAC) complete basis set (CBS-Q) theory prediction (DeltaH(f.298)(0)[CF3-] = -152.6 kcal/mol). We find the CBS-Q prediction of DeltaH(f.298)(0)[CF3] = -112.1 kcal/mol, after BAC, to be in excellent agreement with the most recent experimental determination of the radical heat of formation. The photoelectron angular distribution at 355 nm was also extracted from the photoelectron image, revealing p wave photodetachment with an energy-averaged anisotropy parameter of beta = 1.5 +/- 0.1.
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页码:552 / 557
页数:6
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