The non-relativistic large-Z expansion of the exchange energy of neutral atoms provides an important input to modern non-empirical density functional approximations. Recent works report results of fitting the terms beyond the dominant term, given by the local density approximation (LDA), leading to an anomalous Z ln Z term that cannot be predicted from naïve scaling arguments. Here, we provide much more detailed data analysis of the mostly smooth asymptotic trend describing the difference between exact and LDA exchange energy, the nature of oscillations across rows of the Periodic Table, and the behavior of the LDA contribution itself. Special emphasis is given to the successes and difficulties in reproducing the exchange energy and its asymptotics with existing density functional approximations.

1.
B.-G.
Englert
,
Semiclassical Theory of Atoms
, Lecture Notes in Physics Vol.
300
(Springer Verlag, Berlin,
1988
).
2.
L. H.
Thomas
,
Math. Proc. Camb. Phil. Soc.
23
,
542
(
1927
).
3.
E.
Fermi
,
Z. Phys. A: Hadrons Nucl.
48
,
73
(
1928
).
4.
D.
Lee
,
L. A.
Constantin
,
J. P.
Perdew
, and
K.
Burke
,
J. Chem. Phys.
130
,
034107
(
2009
).
5.
E.
Lieb
and
B.
Simon
,
Phys. Rev. Lett.
31
,
681
(
1973
).
6.
E. H.
Lieb
and
B.
Simon
,
Adv. Math.
23
,
22
(
1977
).
7.
W.
Kohn
and
L. J.
Sham
,
Phys. Rev.
140
,
A1133
(
1965
).
9.
J.
Conlon
,
Commun. Math. Phys.
88
,
133
(
1983
).
10.
P.
Elliott
and
K.
Burke
,
Can. J. Chem.
87
,
1485
(
2009
).
11.
H.
Kunz
and
R.
Rueedi
,
Phys. Rev. A
81
,
032122
(
2010
).
12.
K.
Burke
,
A.
Cancio
,
T.
Gould
, and
S.
Pittalis
,
J. Chem. Phys.
145
,
054112
(
2016
).
13.
A.
Cancio
,
G. P.
Chen
,
B. T.
Krull
, and
K.
Burke
,
J. Chem. Phys.
149
,
084116
(
2018
).
14.
S.
Crisostomo
,
R.
Pederson
,
J.
Kozlowski
,
B.
Kalita
,
A.
Cancio
,
K.
Datchev
,
A.
Wasserman
,
S.
Song
, and
K.
Burke
,
Lett. Math. Phys.
113
,
42
(
2023
).
15.
P. A. M.
Dirac
,
Math. Proc. Cambridge Philos. Soc.
26
,
376
(
1930
).
16.
J. P.
Perdew
,
A.
Ruzsinszky
,
G. I.
Csonka
,
O. A.
Vydrov
,
G. E.
Scuseria
,
L. A.
Constantin
,
X.
Zhou
, and
K.
Burke
,
Phys. Rev. Lett.
100
,
136406
(
2008
).
17.
J.
Sun
,
A.
Ruzsinszky
, and
J. P.
Perdew
,
Phys. Rev. Lett.
115
,
036402
(
2015
).
18.
B.-G.
Englert
and
J.
Schwinger
,
Phys. Rev. A
32
,
47
(
1985
).
19.
J. P.
Perdew
,
L. A.
Constantin
,
E.
Sagvolden
, and
K.
Burke
,
Phys. Rev. Lett.
97
,
223002
(
2006
).
20.
T. J.
Daas
,
D. P.
Kooi
,
A. J. A. F.
Grooteman
,
M.
Seidl
, and
P.
Gori-Giorgi
,
J. Chem. Theory Comput.
18
,
1584
(
2022
).
21.
N.
Argaman
,
J.
Redd
,
A. C.
Cancio
, and
K.
Burke
,
Phys. Rev. Lett.
129
,
153001
(
2022
).
22.
K. J.
Daas
,
D. P.
Kooi
,
T.
Benyahia
,
M.
Seidl
, and
P.
Gori-Giorgi
,
J. Chem. Phys.
159
,
234114
(
2023
).
23.
P.
Svendsen
and
U.
von Barth
,
Phys. Rev. B
54
,
17402
(
1996
).
24.
O. J.
Heilmann
and
E. H.
Lieb
,
Phys. Rev. A
52
,
3628
(
1995
).
25.
P.
Elliott
,
D.
Lee
,
A.
Cangi
, and
K.
Burke
,
Phys. Rev. Lett.
100
,
256406
(
2008
).
26.
B.-G.
Englert
and
J.
Schwinger
,
Phys. Rev. A
26
,
2322
(
1982
).
27.
B.-G.
Englert
and
J.
Schwinger
,
Phys. Rev. A
32
,
26
(
1985
).
28.
C.
Fefferman
and
L.
Seco
,
Adv. Math.
107
,
1
(
1994
).
29.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
,
3865
(
1996
);
[PubMed]
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
78
,
1396(E)
(
1997
).
31.
R. M.
Dreizler
and
E. K. U.
Gross
,
Density Functional Theory: An Approach to the Quantum Many-Body Problem
(
Springer-Verlag
,
Berlin
,
1990
), ISBN: 0387519939.
32.
P.
Okun
and
K.
Burke
,
Semiclassics: The Hidden Theory behind the Success of DFT
(
World Scientific
,
2023
).
33.
J.
Scott
,
London, Edinburgh Dublin Philos. Mag. J. Sci.
43
,
859
(
1952
).
35.
M.
Fuchs
and
M.
Scheffler
,
Comput. Phys. Commun.
119
,
67
(
1999
).
36.
J.
Tao
,
J. P.
Perdew
,
V. N.
Staroverov
, and
G. E.
Scuseria
,
Phys. Rev. Lett.
91
,
146401
(
2003
).
37.
T.
Aschebrock
and
S.
Kümmel
,
Phys. Rev. Res.
1
,
033082
(
2019
).
38.
J. W.
Furness
,
A. D.
Kaplan
,
J.
Ning
,
J. P.
Perdew
, and
J.
Sun
,
J. Phys. Chem. Lett.
11
,
8208
(
2020
);
[PubMed]
J. W.
Furness
,
A. D.
Kaplan
,
J.
Ning
,
J. P.
Perdew
, and
J.
Sun
,
Erratum,
11
,
9248
(
2009
).
39.
J.
Sun
,
J. P.
Perdew
, and
A.
Ruzsinszky
,
Proc. Natl. Acad. Sci. U. S. A.
112
,
685
(
2015
).
40.
A. C.
Cancio
and
J. J.
Redd
,
Mol. Phys.
115
,
618
(
2017
).
41.
J. J.
Redd
and
A. C.
Cancio
,
J. Chem. Phys.
155
,
134112
(
2021
).
42.
D.
Kirzhnits
,
Sov. Phys. JETP
5
,
64
(
1957
).
43.
C. H.
Hodges
,
Can. J. Phys.
51
,
1428
(
1973
).
44.
M.
Levy
and
H.
Ou-Yang
,
Phys. Rev. A
38
,
625
(
1988
).

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