Accurate ab initio potential energy surface, dynamics, and thermochemistry of the F+CH4-->HF+CH3 reaction.
An accurate full-dimensional global potential energy surface (PES) for the F+CH(4)-->HF+CH(3) reaction has been developed based on 19 384 UCCSD(T)/aug-cc-pVTZ quality ab initio energy points obtained by an efficient composite method employing explicit UCCSD(T)/aug-cc-pVDZ and UMP2/aug-cc-pVXZ [X=D,T] computations. The PES contains a first-order saddle point, (CH(4)- -F)(SP), separating reactants from products, and also minima describing the van der Waals complexes, (CH(4)- - -F)(vdW) and (CH(3)- - -HF)(vdW), in the entrance and exit channels, respectively. The structures of these stationary points, as well as those of the reactants and products have been computed and the corresponding energies have been determined using basis set extrapolation techniques considering (a) electron correlation beyond the CCSD(T) level, (b) effects of the scalar relativity and the spin-orbit couplings, (c) diagonal Born-Oppenheimer corrections (DBOC), and (d) zero-point vibrational energies and thermal correction to the enthalpy at 298 K. The resulting saddle point barrier and ground state vibrationally adiabatic barrier heights (V(SP) and V(VAGS)), dissociation energy of (CH(3)- - -HF)(vdW) (D(e) and D(0)), and the reaction enthalpy (DeltaH(e) ( degrees ), DeltaH(0) ( degrees ), and DeltaH(298) ( degrees )) are (240+/-40 and 245+/-200 cm(-1)), (1070+/-10 and 460+/-50 cm(-1)), and (-10000+/-50, -11200+/-80, and -11000+/-80 cm(-1)), respectively. Variational vibrational calculations have been carried out for (CH(3)- - -HF)(vdW) in full (12) dimensions. Quasiclassical trajectory calculations of the reaction using the new PES are reported. The computed HF vibrational and rotational distributions are in excellent agreement with experiment.
Czakó
Gábor
G
Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA. czako@chem.elte.hu
Shepler
Benjamin C
BC
Braams
Bastiaan J
BJ
Bowman
Joel M
JM