We have assessed the degree to which bulk, condensed-phase environments affect the structural properties of FCH2CN-�BF3 and ClCH2CN�BF3 using both low-temperature IR and computations. We have obtained the infrared spectra of both complexes in solid nitrogen, and have assigned the B-F asymmetric stretching and BF3 �umbrella� modes, and they are shifted from those of the gas-phase structure.  Experiments in solid neon and argon are in progress. In addition, we have mapped the B-N bond potential using both DFT and post-HF methods and modeled the effects of the bulk, condensed phase media using the PCM model. The potentials are flat such that the inner, bonded region lies only 3-5 kcal/mol above the global minimum (~2.4 �). However, preferential solvation of the inner region causes the minimum to shift inwards with increasing dielectric constant.  Both experiment and theory indicate that inert matrix environment significantly affects the structures of these complexes.

Condensed-phase effects on the structural properties of FCH2CN-BF3 and ClCH2CN-BF3

245th National Meeting (2013)

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