Department of Chemistry and Rice Quantum Institute, Rice University, Houston, Texas 77251, USA.
J Chem Phys. 2010 Jan 28;132(4):044307. doi: 10.1063/1.3299280.
Fast potassium atoms donate an electron to CCl(3)NO(2) molecules to form K(+) ions and the negative ions O(-), Cl(-), NO(2) (-), CCl(3) (-), CCl(2)NO(2) (-), CCl(3)NO(-), and CCl(3)NO(2) (-). Threshold energies are measured for these ions and electron affinities for CCl(2)NO(2) (-), CCl(3)NO(-), and CCl(3)NO(2) (-) are estimated to be 2.35, 2.35, and 1.89 eV (+/-0.6 eV), respectively. The threshold energies show that the C-N and N-O bonds are substantially weaker than in nitromethane. The CCl(3)NO(2) molecules are oriented before the collision and at energies near 2.5 eV the electron appears to transfer to the pi( *) (NO) orbital forming the parent negative ion, CCl(3)NO(2) (-), which is stabilized by interacting with the K(+) donor. As the collision energy increases the parent negative ion fragments and the orientation dependence of the fragment ions helps understand the fragmentation pathway.
快速钾原子将一个电子捐赠给 CCl(3)NO(2)分子，形成 K(+)离子和负离子 O(-)、Cl(-)、NO(2) (-)、CCl(3) (-)、CCl(2)NO(2) (-)、CCl(3)NO(-)和 CCl(3)NO(2) (-)。测量了这些离子的阈能，并估计 CCl(2)NO(2) (-)、CCl(3)NO(-)和 CCl(3)NO(2) (-)的电子亲和能分别为 2.35、2.35 和 1.89 eV(+/-0.6 eV)。阈能表明 C-N 和 N-O 键比硝基甲烷弱得多。CCl(3)NO(2)分子在碰撞前取向，在接近 2.5 eV 的能量下，电子似乎转移到 pi( *) (NO)轨道，形成母体负离子 CCl(3)NO(2) (-)，它通过与 K(+)供体相互作用而稳定。随着碰撞能的增加，母体负离子碎片和碎片离子的取向依赖性有助于理解碎片途径。
