minor edits

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Hugh Burton 2020-11-30 21:34:39 +00:00
parent cf629c78c2
commit 4fff7c9fd2

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@ -1295,11 +1295,11 @@ orbitals [see Eq.~\eqref{eq:RHF_orbs}] with $\theta_{\alpha}^{\text{RHF}} = \the
%\begin{equation}
% E_\text{HF}(0, 0) = \frac{1}{2} (2 U - 4 \epsilon).
%\end{equation}
With this representation, the parametrised RMP Hamiltonian becomes
With this representation, the parametrised \hugh{atomic} RMP Hamiltonian becomes
\begin{widetext}
\begin{equation}
\label{eq:H_RMP}
\bH_\text{RMP}\qty(\lambda) =
\hugh{\bH_\text{atom}\qty(\lambda)} =
\begin{pmatrix}
2(U-\epsilon) - \lambda U & -\lambda t & -\lambda t & 0 \\
-\lambda t & (U-\epsilon) - \lambda U & 0 & -\lambda t \\
@ -1337,7 +1337,8 @@ In contrast, smaller $\epsilon$ gives a weaker attraction to the atomic site,
representing strong screening of the nuclear attraction by core and valence electrons,
and again a less negative $\lambda$ is required for ionisation to occur.
Both of these factors are common in atoms on the right-hand side of the periodic table, \eg\ \ce{F},
\ce{O}, \ce{Ne}, and thus molecules containing these atoms are often class $\beta$ systems with
\ce{O}, \ce{Ne}.
Molecules containing these atoms are therefore often class $\beta$ systems with
a divergent RMP series due to the MP critical point. \cite{Goodson_2004,Sergeev_2006}
% EXACT VERSUS APPROXIMATE
@ -1384,10 +1385,9 @@ For $\lambda>1$, the HF potential becomes an attractive component in Stillinger'
Hamiltonian displayed in Eq.~\eqref{eq:HamiltonianStillinger}, while the explicit electron-electron interaction
becomes increasingly repulsive.
Critical points along the positive real $\lambda$ axis for closed-shell molecules then represent
points where the two-electron repulsion overcomes the attractive HF potential and an electron
are successively expelled from the molecule.\cite{Sergeev_2006}
points where the two-electron repulsion overcomes the attractive HF potential and a single electron dissociates from the molecule.\cite{Sergeev_2006}
Symmetry-breaking in the UMP reference creates different HF potentials for the spin-up and spin-down electrons.
In contrast, symmetry-breaking in the UMP reference creates different HF potentials for the spin-up and spin-down electrons.
Consider the reference UHF solution where the spin-up and spin-down electrons are localised on the left and
right sites respectively.
The spin-up HF potential will then be a repulsive interaction from the spin-down electron
@ -1413,7 +1413,7 @@ occurs exactly at $\lambda = 1$.
In this limit, the ground-state EPs approach the real axis (Fig.~\ref{subfig:ump_ep_to_cp}) and the avoided
crossing creates a gradient discontinuity in the ground-state energy (dashed lines in Fig.~\ref{subfig:ump_cp}).
We therefore find that, in the strong correlation limit, the symmetry-broken ground-state EP becomes
a new type of MP critical and represents a QPT in the perturbation approximation.
a new type of MP critical point and represents a QPT in the perturbation approximation.
Furthermore, this argument explains why the dominant UMP singularity lies so close, but always outside, the
radius of convergence (see Fig.~\ref{fig:RadConv}).