The unsolved issue with out-of-plane bending frequencies for CC multiply bonded systems

More than 30 years ago two groups independently identified a problem in the calculation of the out-of-plane bending (OPB) vibrational frequencies for the ethylene molecule using correlated electronic structure methods. Several studies have been done in the meantime to try and understand and resolve this issue. In so doing this problem has been found to be far more insidious than previously realized for acetylene-like and benzene-like molecules, which can become non-linear and non-planar, respectively. The one common feature that all molecules with this problem have is that they contain CC multiple bonds, and so this has been called the "CC multiple bond OPB frequency issue" or "the CC OPB problem." Various explanations for this problem have been advanced such as basis set superposition error, basis set incompleteness error, linear dependences in the basis set, proper balancing of the basis set between saturation and inclusion of higher angular momentum functions, etc. and possible solutions have arisen from these suggestions. All of these proposed solutions, however, amount to one main point connecting them all: modifying the one-particle basis set in some way. None of the explanations that have been advanced, however, really fit all of the data for all of the molecules where this problem has been identified, and importantly, none of these diagnostic tests have been applied to similar molecules where this issue does not appear. In this review, the studies over the last 30 plus years are discussed and relevant data from each of these is compared and contrasted. It is hoped that by collecting and analyzing the data from these studies a path forward to understanding and resolving this issue will become evident.