Thursday 28 August 2014

Multireference spin-orbit configuration interaction - perturbational treatment

If you are interested in multireference methods and/or relativistic effects, here is a new paper for you: "Perturbational treatment of spin-orbit coupling for generally applicable high-level multi-reference methods" in J. Chem. Phys. What we did is taking the existing spin-orbit CI code in Columbus and extended it for quasi-degenerate perturbation theory, which is in fact just a fancy way of saying that we stop the MR-CI after the first iteration (using the non-relativistic solutions as initial guesses). Besides that we needed an interface translating the CI vectors between the non-relativistic and relativistic representations.

With this tool we could compare the perturbational treatment with the full SO-CI. The agreement of the relative energies was quite good. But there was a significant difference in the total energies, since spin polarization was missing in the perturbational model space. But this was a systematic error affecting all states more or less the same.

The main reason why we wanted the perturbational approach is that it allows for the computation of gradients and non-adiabatic interactions (assuming that the spin-orbit couplings are slowly varying). And then we can do non-adiabatic dynamics with it. So far the methodology is implemented in SHARC with an application in this paper.

And finally, since they always look cool, a representation of the Shavitt graph coding the SO-CI configurations:

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