The argon matrix-induced frequency shift of ν_s(F-H) of the F-H···A complexes: Comparison between computation and experiment

摘要

The experimental argon matrix-induced frequency shifts of the νs(F-H) of the complexes F-H···FH, F-H···CO, and F-H···NCH have been simulated extremely well within the framework of polarizable continuum model with integral equation formalism (IEF-PCM) at the B3LYP level of theory with the basis sets 6-311++G(df,pd), 6-311++G(2df,2pd), and 6-311++G(3df,3pd). For the complexes Cl-H···NCCH3 and F-H···NH3, the MP2 simulated (also within the framework of IEF-PCM) shifts of the νs(X-H) (X = F, Cl) are also in excellent agreement with the experimental ones. Theoretically calculated geometric variations of the F-H (Cl-H) bond length and F···A (Cl···N) distance (sometimes including also the hydrogen bond angle) within the framework of IEF-PCM demonstrate clearly that, for the above five hydrogen-bond complexes, a stronger hydrogen bond and a larger extent of proton sharing have been induced by the argon matrix solvation.