Following the discussion here of Kekulé’s suggestion of what we now call a vibrational mode (and which in fact now bears his name), I thought I might apply the concept to a recent molecule known as [2.2]paracyclophane. The idea was sparked by Steve Bachrach’s latest post, where the “zero-point” structure of the molecule has recently been clarified as having D2 symmetry.[1]
Let me start with a ωB97XD/6-311G(d,p) calculation of this mode. Because the mode is a mixture of C and H motions (which differ according to the molecule), I am going to try to normalise the mode by reducing the mass of the all atoms except the core six to effectively zero. The mode itself looks as below with the H-weighting applied. The hydrogens are riding, massless, on each of the six carbons.
The results are presented in the table below for the paracyclophane, in three different spin states.
System | Mass-weighted modes, s, a | Reduced mass, sym | Reduced mass, asym | DOI |
---|---|---|---|---|
Benzene, singlet | 1342 | 1318 | [2] | |
paracyclophane, singlet | 1335, 1330 | 1257 | 1237 | [3] |
paracyclophane, triplet | 1413, 1418 | 1403 | 1394 | [4] |
paracyclophane, quintet | 1566, 1563 | 1521 | 1522 | [5] |
There are three effects which manifest.
Perhaps this cooperation would be even stronger were it not from the distinct distortion from planarity that the cyclophane bridges enforce, and which might discourage the π-tendency to form cyclohexatriene.
My point with this post was to show how interesting new effects can be teased out of systems of contemporary interest by invoking Kekulé’s famous (vibrational) mode. Whether this corresponds to what the man himself had in mind is quite another matter of course.
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