Dynamics of the gas-phase reactions of fluoride ions with chloromethane

Guided ion beam tandem mass spectrometry techniques are used to examine the competing chemical dynamics of reactions of fluoride ions with chlorometha ne in the center-of-mass collision energy range 0.05-30 eV. The exothermic bimolecular nucleophilic substitution (S(N)2) reaction F- + CH3Cl --> CH3F + Cl- predominates at the lowest collision energies (0.05-0.1 eV) but decre ases by a factor of similar to 100 over the range 0.1-2 eV. Two endothermic product channels are detected at collision energies similar to1-20 eV, cor responding to proton transfer to form HF + CH2Cl- and chlorine abstraction to form CH3 + FCl-. The threshold energy for the proton-transfer reaction i s E-0 = 97 +/- 9 kJ/mol, which yields Delta H-acid(298)(CH3Cl) less than or equal to 1653 +/- 9 kJ/mol and EA(0)(CH2Cl) greater than or equal to 0.77 +/- 0.14 eV. The threshold energy for the chlorine abstraction reaction to form FCl- is Eo = 170 +/- 40 kJ/mol, which yields EA(0)(FCl) greater than o r equal to 2.6 +/- 0.4 eV. Potential energy surfaces for the three reaction paths are calculated using the coupled cluster and density functional theo ry methods at the CCSD(T)/aug-cc-pVDZ and B3LYP/aug-cc-pVDZ levels. Geometr y optimizations of stationary points along the surfaces show that a hydroge n-bonded F- . . .H-CH2Cl complex is 5 kJ/mol lower in energy than the C3 up silon F- CH3Cl complex. An additional feature observed in the Cl- reaction cross section at collision energies above 2 eV is attributed to further dis sociation of CH2Cl- and FCl- products.