Electron Transfer Collisions with Oriented Trifluoroacetic Acid (CF3CO2H)

被引:9
作者
Brooks, Philip R. [1 ,2 ]
机构
[1] Rice Univ, Dept Chem, Houston, TX 77005 USA
[2] Rice Univ, Rice Quantum Inst, Houston, TX 77005 USA
基金
美国国家科学基金会;
关键词
FORMIC-ACID; MICROWAVE-SPECTRUM; INTERNAL-ROTATION; ACETIC-ACID; MOLECULES; ATTACHMENT; CH3NO2; NITROMETHANE; POTASSIUM; ATOMS;
D O I
10.1021/jp9029369
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
Electron transfer collisions between neutral K atoms and neutral, oriented trifluoroacetic acid molecules, CF3CO2H, are studied in crossed molecular beams at center of mass energies from 6 to 18 eV. An electron transfer produces a pair of ions with enough energy to escape the Coulomb attraction, and the ions are detected in separate time-of-flight mass spectrometers. The principle ions formed are K+ and the trifluoroacetate ion, CF3CO2- ion, and this channel is favored for attack at the positive (-CO2H) end of the molecule. The steric asymmetry suggests that the electron is transferred into the pi(co)* orbital. The nascent K+ perturbs the molecular symmetry, allowing electron migration to the sigma(OH)* orbital to break the O-H bond and form CF3CO2-.
引用
收藏
页码:14296 / 14301
页数:6
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