An experimental and theoretical study of the reactions Na+HCl and Na+DCl

摘要: An experimental study is presented of the reactions Na+HCl/DCl from 590 to 820 K. Na atoms were produced in an excess HCl/DCl and He bath gas, by pulsed photolysis NaCl vapor. The metal atom concentration was then monitored time‐resolved laser induced fluorescence at λ=589 nm. A fit data Arrhenius form yields (2σ uncertainty): k(Na+HCl)=(2.1±0.5)×10−9 exp[(−41.8±1.5 kJ mol−1)/RT] cm3  molecule−1 s−1; k(Na+DCl)=(2.2±1.0)×10−9 exp[(−45.5±3.8  molecule−1 s−1. large activation energies are shown be consistent with vibrational excitation hydrogen halides greatly enhancing reaction cross‐sections. pair ab initio potential surfaces for these calculated constant angle cuts through lowest 2 A’ hypersurface, including a collinear surface containing saddle point which found occur bent configuration θNaClH=54.7°. Both exhibit late barrier. effect ...