quick revision and letter
This commit is contained in:
parent
8efc787470
commit
78389680e6
@ -392,6 +392,7 @@ These degeneracies can be conical intersections between two states with differen
|
||||
for real values of $\lambda$,\cite{Yarkony_1996} or EPs between two states with the
|
||||
same symmetry for complex values of $\lambda$.
|
||||
|
||||
\titou{Although the complex component of the energy is linked to lifetime in non-Hermitian quantum mechanics, \cite{MoiseyevBook} its meaning is unclear to us in the present context.}
|
||||
|
||||
%============================================================%
|
||||
\subsection{Rayleigh--Schr\"odinger Perturbation Theory}
|
||||
@ -783,7 +784,7 @@ diatomics, where low-order RMP and UMP expansions give qualitatively wrong bindi
|
||||
The divergence of RMP expansions for stretched bonds can be easily understood from two perspectives.\cite{Gill_1988a}
|
||||
Firstly, the exact wave function becomes increasingly multi-configurational as the bond is stretched, and the
|
||||
RHF wave function no longer provides a qualitatively correct reference for the perturbation expansion.
|
||||
Secondly, the energy gap between the bonding and anti-bonding orbitals associated with the stretch becomes
|
||||
Secondly, the energy gap between the \titou{occupied and unoccupied} orbitals associated with the stretch becomes
|
||||
increasingly small at larger bond lengths, leading to a divergence, for example, in the MP2 correction \eqref{eq:EMP2}.
|
||||
In contrast, the origin of slow UMP convergence is less obvious as the reference UHF energy remains
|
||||
qualitatively correct at large bond lengths and the orbital degeneracy is avoided.
|
||||
@ -891,12 +892,12 @@ The Taylor expansion of the RMP energy can then be evaluated to obtain the $k$th
|
||||
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
||||
% RADIUS OF CONVERGENCE PLOTS
|
||||
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
|
||||
The RMP series is convergent for $U = 3.5\,t$ with $\rc > 1$, as illustrated for the individual terms at each
|
||||
The RMP series is convergent \titou{at $\lambda = 1$} for $U = 3.5\,t$ with $\rc > 1$, as illustrated for the individual terms at each
|
||||
perturbation order in Fig.~\ref{subfig:RMP_cvg}.
|
||||
In contrast, for $U = 4.5t$ one finds $\rc < 1$, and the RMP series becomes divergent.
|
||||
In contrast, for $U = 4.5t$ one finds $\rc < 1$, and the RMP series becomes divergent \titou{at $\lambda = 1$}.
|
||||
The corresponding Riemann surfaces for $U = 3.5\,t$ and $4.5\,t$ are shown in Figs.~\ref{subfig:RMP_3.5} and
|
||||
\ref{subfig:RMP_4.5}, respectively, with the single EP at $\lep$ (black dot) and the radius of convergence indicated
|
||||
by the vertical cylinder of unit radius.
|
||||
\ref{subfig:RMP_4.5}, respectively, with the single EP at $\lep$ (black dot) and \titou{the radius of convergence indicated
|
||||
by the vertical cylinder of unit radius (TODO)}.
|
||||
For the divergent case, $\lep$ lies inside this cylinder of convergence, while in the convergent case $\lep$ lies
|
||||
outside this cylinder.
|
||||
In both cases, the EP connects the ground state with the doubly-excited state, and thus the convergence behaviour
|
||||
@ -966,7 +967,7 @@ The convergence behaviour can be further elucidated by considering the full stru
|
||||
in the complex $\lambda$-plane (see Figs.~\ref{subfig:UMP_3} and \ref{subfig:UMP_7}).
|
||||
These Riemann surfaces are illustrated for $U = 3t$ and $7t$ alongside the perturbation terms at each order
|
||||
in Fig.~\ref{subfig:UMP_cvg}.
|
||||
At $U = 3t$, the RMP series is convergent, while RMP becomes divergent for $U=7t$.
|
||||
At $U = 3t$, the RMP series is convergent \titou{at $\lambda = 1$}, while RMP becomes divergent \titou{at $\lambda = 1$} for $U=7t$.
|
||||
The ground-state UMP expansion is convergent in both cases, although the rate of convergence is significantly slower
|
||||
for larger $U/t$ as the radius of convergence becomes increasingly close to one (Fig.~\ref{fig:RadConv}).
|
||||
|
||||
@ -1073,7 +1074,7 @@ The authors first considered molecules with low-lying doubly-excited states with
|
||||
and spin symmetry as the ground state. \cite{Olsen_2000}
|
||||
In these systems, the exact wave function has a non-negligible contribution from the doubly-excited states,
|
||||
and thus the low-lying excited states are likely to become intruder states.
|
||||
For \ce{CH_2} in a diffuse, yet rather small basis set, the series is convergent at least up to the 50th order, and
|
||||
For \ce{CH_2} in a diffuse, yet rather small basis set, the series is convergent \titou{at $\lambda = 1$} at least up to the 50th order, and
|
||||
the dominant singularity lies close (but outside) the unit circle, causing slow convergence of the series.
|
||||
These intruder-state effects are analogous to the EP that dictates the convergence behaviour of
|
||||
the RMP series for the Hubbard dimer (Fig.~\ref{fig:RMP}).
|
||||
@ -1278,7 +1279,7 @@ The RMP critical point then corresponds to the intersection $E_{-} = E_{+}$, giv
|
||||
\lc = 1 - \frac{\epsilon}{U}.
|
||||
\end{equation}
|
||||
Clearly the radius of convergence $\rc = \abs{\lc}$ is controlled directly by the ratio $\epsilon / U$,
|
||||
with a convergent RMP series occurring for $\epsilon > 2 U$.
|
||||
with a convergent RMP series \titou{at $\lambda = 1$} occurring for $\epsilon > 2 U$.
|
||||
The on-site repulsion $U$ controls the strength of the HF potential localised around the ``atomic site'', with a
|
||||
stronger repulsion encouraging the electrons to be ionised at a less negative value of $\lambda$.
|
||||
Large $U$ can be physically interpreted as strong electron repulsion effects in electron dense molecules.
|
||||
|
@ -72,9 +72,11 @@ We look forward to hearing from you.
|
||||
This is hinted at in the introduction but was the first question that entered my mind.}
|
||||
\\
|
||||
\alert{In most figures, we indeed plot the real component of the energy.
|
||||
By going complex, the energies lost their meaning as there's no relation of order for complex numbers.
|
||||
By going complex, the energies lost their meaning as there is no relation of order for complex numbers.
|
||||
In non-Hermitian processes like resonances or scattering, the imaginary part of the energy is indeed linked to lifetimes [see the book of Moiseyev].
|
||||
However, the meaning of the imaginary part of the energy in the present context is unclear and we prefer not to speculate on this.}
|
||||
This is mention in the introduction section.
|
||||
However, the meaning of the imaginary part of the energy in the present context is unclear and we prefer not to speculate on this.
|
||||
We have added a comment on this point in the revised version of the manuscript.}
|
||||
|
||||
\item
|
||||
{IIe.\\
|
||||
@ -94,7 +96,7 @@ We look forward to hearing from you.
|
||||
Also, in the general case (either RHF or UHF), the bonding orbitals for the two sigma values are occupied and the two antibonding orbitals are unoccupied.
|
||||
Bonding and antibonding notation is not so common in the condensed matter literature and it may be missed that these correspond to occupied and empty single-particle states.}
|
||||
\\
|
||||
\alert{We now mention that Eqs. 20, 21a, and 21b are valid for both the RHF and UHF cases.
|
||||
\alert{We now mention that Eqs. 20, 21a, and 21b are valid for both RHF and UHF.
|
||||
We have also changed the notations for the occupied and empty single-particle states.}
|
||||
|
||||
\item
|
||||
@ -106,7 +108,7 @@ We look forward to hearing from you.
|
||||
Certain values away from $\lambda=1$ can also have physical meaning, like the autoionization process discussed later.}
|
||||
\\
|
||||
\alert{Only the $\lambda = 0$ (non-interacting system in some cases) and $\lambda = 1$ (fully interacting system) are physical systems as mentioned in the manuscript.
|
||||
However, it can be useful to study the systems at different $\lambda$ values.}
|
||||
However, it can be useful to study the systems at different $\lambda$ values as we do in Sec.~II.F.}
|
||||
|
||||
\item
|
||||
{IIIc.\\
|
||||
@ -116,7 +118,7 @@ We look forward to hearing from you.
|
||||
I first thought the cylinder was marking the radius of convergence. It is meant to show the position of the EPs and indicate if the radius of convergence is $>1$ or $<1$.
|
||||
The language could be improved.}
|
||||
\\
|
||||
\alert{The language has been improved.}
|
||||
\alert{The language has been improved and we have mentioned in several places that we are talking about a convergent/divergent MP series at $\lambda = 1$.}
|
||||
|
||||
\item
|
||||
{IIId.\\
|
||||
@ -124,7 +126,7 @@ We look forward to hearing from you.
|
||||
I raise this point because the journal is JPCM, and these terms are not common in condensed matter literature.
|
||||
Are intruder states equivalent to states creating exceptional points that ruin the series convergence?}
|
||||
\\
|
||||
\alert{The classification of front-door and back-door intruder states have been clarified.
|
||||
\alert{We believe that the classification of front-door and back-door intruder states has been clearly defined in the original manuscript:
|
||||
"Following this theory, a singularity in the unit circle is designated as an intruder state, with a front-door (or back-door) intruder state if the real part of the singularity is positive (or negative)."}
|
||||
|
||||
\item
|
||||
|
Loading…
Reference in New Issue
Block a user