Henry Rzepa's Blog Chemistry with a twist

April 25, 2019

Imaging normal vibrational modes of a single molecule of CoTPP: a mystery about the nature of the imaged species.

Previously, I explored (computationally) the normal vibrational modes of Co(II)-tetraphenylporphyrin (CoTPP) as a “flattened” species on copper or gold surfaces for comparison with those recently imaged[1]. The initial intent was to estimate the “flattening” energy. There are six electronic possibilities for this molecule on a metal surface. Respectively positively, or negatively charged and a neutral species, each in either a low or a high-spin electronic state. I reported five of these earlier, finding each had quite high barriers for “flattening” the molecule. For the final 6th possibility, the triplet anion, the SCF (self-consistent-field) had failed to converge, but for which I can now report converged results.

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References

  1. J. Lee, K.T. Crampton, N. Tallarida, and V.A. Apkarian, "Visualizing vibrational normal modes of a single molecule with atomically confined light", Nature, vol. 568, pp. 78-82, 2019. http://dx.doi.org/10.1038/s41586-019-1059-9

June 13, 2016

A wider look at π-complex metal-alkene (and alkyne) compounds.

Previously, I looked at the historic origins of the so-called π-complex theory of metal-alkene complexes. Here I follow this up with some data mining of the crystal structure database for such structures.

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February 9, 2016

Bond stretch isomerism. Did this idea first surface 100 years ago?

The phenomenon of bond stretch isomerism, two isomers of a compound differing predominantly in just one bond length, is one of those chemical concepts that wax and occasionally wane.[1] Here I explore such isomerism for the elements Ge, Sn and Pb.

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References

  1. J.A. Labinger, "Bond-stretch isomerism: a case study of a quiet controversy", Comptes Rendus Chimie, vol. 5, pp. 235-244, 2002. http://dx.doi.org/10.1016/S1631-0748(02)01380-2

May 30, 2015

Discovering chemical concepts from crystal structure statistics: The Jahn-Teller effect

I am on a mission to persuade my colleagues that the statistical analysis of crystal structures is a useful teaching tool.  One colleague asked for a demonstration and suggested exploring the classical Jahn-Teller effect (thanks Milo!). This is a geometrical distortion associated with certain molecular electronic configurations, of which the best example is illustrated by octahedral copper complexes which have a d9 electronic configuration. The eg level shown below is occupied by three electrons and which can therefore distort in one of two ways to eliminate the eg degeneracy by placing the odd electron into either a x2-y2 or a z2 orbital. Here I explore how this effect can be teased out of crystal structures.

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