Sunday, January 24, 2016

A Practicable Real-Space Measure and Visualization of Static Electron-Correlation Effects

Grimme, S.; Hansen, A. Angew. Chem. Int. Ed. 2015, 54, 12308-12313
Contributed by Steven Bachrach
Reposted from Computational Organic Chemistry with permission

Assessing when a molecular system might be subject to sizable static (non-dynamic) electron correlation, necessitating a multi-reference quantum mechanical treatment, is perhaps more art than science. In general one suspects that static correlation will be important when the frontier MO energy gap is small, but is there a way to get more guidance?

Grimme reports the use of fractional occupancy density (FOD) as a visualization tool to identify regions within molecules that demonstrate significant static electron correlation.1 The method is based on the use of finite temperature DFT.2,3

The resulting plots of the FOD for a series of test cases follow our notions of static correlation. Molecules, such as alkanes, simple aromatics, and concerted transition states show essentially no fractional orbital density. On the other hand, the FOD plot for ozone shows significant density spread over the entire molecule; the transition state for the cleavage of the terminal C-C bond in octane shows FOD at C1 and C2but not elsewhere; p-benzyne shows significant FOD at the two radical carbons, while the FOD is much smaller in m-benzyne and is negligible in o-benzyne.
This FOD method looks to be a simple tool for evaluating static correlation and is worth further testing.


References

(1) Grimme, S.; Hansen, A. "A Practicable Real-Space Measure and Visualization of Static Electron-Correlation Effects," Angew. Chem. Int. Ed. 201554, 12308-12313, DOI: 10.1002/anie.201501887.
(2) Mermin, N. D. "Thermal Properties of the Inhomogeneous Electron Gas," Phys. Rev. 1965137, A1441-A1443, DOI: 10.1103/PhysRev.137.A1441.
(3) Chai, J.-D. "Density functional theory with fractional orbital occupations," J. Chem. Phys 2012136, 154104, DOI: doi: 10.1063/1.3703894.

[Editors note: this paper has also been highlighted by Tobias Schwabe]


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