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

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.