On the interactions of nitriles and fluoro-substituted pyridines with silicon tetrafluoride: Computations and thin film IR spectroscopy

Structural and energetic properties of RMX3‐NH3 complexes

“…This may be due, in part, to isotopic composition; the predictions are strictly for 74 Ge isotopomer, while the measured frequencies reflect an average of five naturally occurring isotopes of germanium. It is worth noting that we have also found M06 to be optimal in two recent studies of related MF 4 complexes, [ 24,25 ] in which we used a similar validation procedure. In all cases, the goal is to make effective comparisons between the experimental and theoretical frequencies of the various complexes (vide infra).…”

“…Subsequent studies of nitrogen‐donor‐MX 4 complexes (M=Si, Ge, Ti; X=F, Cl) [ 23–25 ] revealed some indication of condensed‐phase structural changes, but overall, those were much less dramatic than the observations noted above for the B‐N systems. One striking example was CH 3 CN–SiF 4 , for which a theory predicted a long gas‐phase Si‐N distance of about 3.0 Å that would shorten by over 1.0 Å in low‐dielectric media (ε=5).…”

“…However, no experimental evidence of this extraordinary structural change could be observed via low‐temperature IR spectroscopy measurements. [ 23 ] More subtle effects were predicted for both nitrile‐GeF 4 [ 23,24 ] and imine‐SiF 4 complexes, [ 25 ] but a complicating factor with these systems is that the stable reaction products that result from the direct mixing of donor and acceptor are a 2:1 complexes (eg, GeF 4 (NCCH 3 ) 2 ) with a six‐coordinate metal. This obscures any direct comparisons to the solid state with regard to the analogous 1:1 system.…”

Twenty years of exceptional success: The molecular education and research consortium in undergraduate computational chemistry (MERCURY)

“…The faculty published 2 peer‐reviewed books, [ 238,239 ] 9 peer‐reviewed book chapters, [ 240–248 ] and 115 peer‐reviewed research papers. [ 249–363 ] This comes to 1.6 peer‐reviewed products/faculty/year during the 3‐year grant period, which is 3.2 times the rate of publication for natural science faculty at PUIs. [ 46 ]…”

“…Computations are vital for characterizing gas‐phase systems and providing direct insight into the mechanism for medium‐induced structural change [ 181,213,393 ] and to enable them to identify promising targets and focus their experimental efforts. [ 181,394,395 ] Following up on their initial work on group IV halides (MX 4 : M = Ti, Si, Ge; X = F, Cl), [ 211,298,310 ] they are exploring the nitrile and imine complexes of the monoalkyl analogs (MX 3 R) of these acids.…”