J. Phys. Chem. A 2003, 107, 11427-11432
11427
Low-Energy Electron Attachment by Chloroalkanes Wiesława Barszczewska, Janina Kopyra, Jolanta Wnorowska, and Iwona Szamrej* Chemistry Department, UniVersity of Podlasie, Siedlce, Poland ReceiVed: May 30, 2003; In Final Form: September 2, 2003
Thermal electron attachment rate constants for 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, 1- and 2-chloropropanes, and 1,1-, 1,2-, 2,2-, and 1,3-dichloropropanes have been measured using an electron swarm method. It has been found that all the investigated compounds attach electrons only in a two-body process. Corresponding rate constants are equal to 1.4 × 10-10, 3.2 × 10-8, 2.7 × 10-13, 3.8 × 10-12, 5.7 × 10-11, 8.1 × 10-12, 6.3 × 10-12, and 1.2 × 10-11 cm3 molecule-1 s-1, respectively. The dependence of the electron capture rate constants on the electronic polarizability of the accepting center of the molecule and the vertical attachment energy has been demonstrated.
Introduction Thermal electron capture processes in the gas phase constitute an important class of chemical reactions. If electron energies are in thermal equilibrium with the surrounding molecules, the rate constant for the electron capture strongly depends on the shape and position of the resonance and its overlap with the Maxwell-Boltzman distribution of the electron and molecule energies.1-3 Hence, the measured rate constants differ by six orders of magnitude (from 10-7 down to
