Friday, November 3, 2017

quantum chemistry - Why is Coupled Cluster not variational?


It has been noted in several sources (e.g. J. Romero et al. Strategies for quantum computing molecular energies using the unitary coupled cluster ansatz. arXiv:1701.02691 [quant-ph]) that one of the disadvantages of the Coupled Cluster method for the description of electron correlation is that, since $e^T$ in $$E_\mathrm{CC} = \langle0|e^{-T}He^T|0\rangle$$ isn't unitary, the method isn't variational (the energy obtained by solving CC equations isn't a rigorous upper bound to the exact energy).


Could someone please explain to me the connection between non-unitarity of $e^T$ and the method not being variational.




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periodic trends - Comparing radii in lithium, beryllium, magnesium, aluminium and sodium ions

Apparently the of last four, $\ce{Mg^2+}$ is closest in radius to $\ce{Li+}$. Is this true, and if so, why would a whole larger shell ($\ce{...