We devise a nonlocal correlation energy functional that describes the entire range of dispersion interactions in a seamless fashion using only the electron density as input. The new functional is considerably simpler than its predecessors of a similar type. The functional has a tractable and robust analytic form that lends itself to efficient self-consistent implementation. When paired with an appropriate exchange functional, our nonlocal correlation model yields accurate interaction energies of weakly-bound complexes, not only near the energy minima but also far from equilibrium. Our model exhibits an outstanding precision at predicting equilibrium intermonomer separations in van der Waals complexes. It also gives accurate covalent bond lengths and atomization energies. Hence the functional proposed in this work is a computationally inexpensive electronic structure tool of broad applicability.

1.
W.
Kohn
and
L. J.
Sham
,
Phys. Rev.
140
,
A1133
(
1965
).
2.
A Primer in Density Functional Theory
, edited by
C.
Fiolhais
,
F.
Nogueira
, and
M.
Marques
(
Springer
,
Berlin
,
2003
).
3.
G. E.
Scuseria
and
V. N.
Staroverov
, in
Theory and Applications of Computational Chemistry: The First Forty Years
, edited by
C. E.
Dykstra
,
G.
Frenking
,
K. S.
Kim
, and
G. E.
Scuseria
(
Elsevier
,
Amsterdam
,
2005
).
4.
K. E.
Riley
,
M.
Pitoňák
,
P.
Jurečka
, and
P.
Hobza
,
Chem. Rev.
110
,
5023
(
2010
).
5.
S.
Grimme
,
J.
Antony
,
S.
Ehrlich
, and
H.
Krieg
,
J. Chem. Phys.
132
,
154104
(
2010
), and references therein.
6.
H.-V.
Nguyen
and
G.
Galli
,
J. Chem. Phys.
132
,
044109
(
2010
).
7.
W.
Zhu
,
J.
Toulouse
,
A.
Savin
, and
J. G.
Ángyán
,
J. Chem. Phys.
132
,
244108
(
2010
).
8.
M.
Dion
,
H.
Rydberg
,
E.
Schröder
,
D. C.
Langreth
, and
B. I.
Lundqvist
,
Phys. Rev. Lett.
92
,
246401
(
2004
).
9.
K.
Lee
,
É. D.
Murray
,
L.
Kong
,
B. I.
Lundqvist
, and
D. C.
Langreth
,
Phys. Rev. B
82
,
081101
(
2010
).
10.
O. A.
Vydrov
and
T.
Van Voorhis
,
J. Chem. Phys.
130
,
104105
(
2009
).
11.
O. A.
Vydrov
and
T.
Van Voorhis
,
Phys. Rev. Lett.
103
,
063004
(
2009
).
12.
D. C.
Langreth
and
B. I.
Lundqvist
,
Phys. Rev. Lett.
104
,
099303
(
2010
);
[PubMed]
O. A.
Vydrov
and
T.
Van Voorhis
,
Phys. Rev. Lett.
104
,
099304
(
2010
).
[PubMed]
13.
O. A.
Vydrov
and
T.
Van Voorhis
,
Phys. Rev. A
81
,
062708
(
2010
).
15.
J. P.
Perdew
,
L. A.
Constantin
,
E.
Sagvolden
, and
K.
Burke
,
Phys. Rev. Lett.
97
,
223002
(
2006
).
16.
O. A.
Vydrov
and
T.
Van Voorhis
,
J. Chem. Phys.
132
,
164113
(
2010
).
17.
B. G.
Johnson
,
P. M. W.
Gill
, and
J. A.
Pople
,
J. Chem. Phys.
98
,
5612
(
1993
).
18.
A. D.
Becke
,
J. Chem. Phys.
88
,
2547
(
1988
).
19.
J. P.
Perdew
and
Y.
Wang
,
Phys. Rev. B
33
,
8800
(
1986
).
20.
D. J.
Lacks
and
R. G.
Gordon
,
Phys. Rev. A
47
,
4681
(
1993
).
21.
F. O.
Kannemann
and
A. D.
Becke
,
J. Chem. Theory Comput.
5
,
719
(
2009
);
[PubMed]
F. O.
Kannemann
and
A. D.
Becke
,
J. Chem. Theory Comput.
6
,
1081
(
2010
).
22.
E. D.
Murray
,
K.
Lee
, and
D. C.
Langreth
,
J. Chem. Theory Comput.
5
,
2754
(
2009
).
23.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
,
3865
(
1996
).
24.
The value of C = 0.0089 was obtained in Ref. 11 by fitting to a
$C_6$
C6
test set using electron densities produced by the long-range corrected (LC) hybrid functional LC-ωPBE. As compared to LC hybrids, the description of density tails by semilocal XC functionals is systematically less accurate, which is reflected in
$\omega _g$
ωg
. The readjusted value of C = 0.0093 is tailored for use with semilocal XC functionals, such as rPW86-PBE.
25.
P.
Jurečka
,
J.
Šponer
,
J.
Černý
, and
P.
Hobza
,
Phys. Chem. Chem. Phys.
8
,
1985
(
2006
).
26.
Y.
Shao
,
L.
Fusti-Molnar
,
Y.
Jung
,
J.
Kussmann
,
C.
Ochsenfeld
,
S. T.
Brown
,
A. T. B.
Gilbert
,
L. V.
Slipchenko
,
S. V.
Levchenko
,
D. P.
O'Neill
,
R. A.
DiStasio
 Jr.
,
R. C.
Lochan
,
T.
Wang
,
G. J. O.
Beran
,
N. A.
Besley
,
J. M.
Herbert
,
C. Y.
Lin
,
T.
Van Voorhis
,
S. H.
Chien
,
A.
Sodt
,
R. P.
Steele
,
V. A.
Rassolov
,
P. E.
Maslen
,
P. P.
Korambath
,
R. D.
Adamson
,
B.
Austin
,
J.
Baker
,
E. F. C.
Byrd
,
H.
Dachsel
,
R. J.
Doerksen
,
A.
Dreuw
,
B. D.
Dunietz
,
A. D.
Dutoi
,
T. R.
Furlani
,
S. R.
Gwaltney
,
A.
Heyden
,
S.
Hirata
,
C.-P.
Hsu
,
G.
Kedziora
,
R. Z.
Khalliulin
,
P.
Klunzinger
,
A. M.
Lee
,
M. S.
Lee
,
W.
Liang
,
I.
Lotan
,
N.
Nair
,
B.
Peters
,
E. I.
Proynov
,
P. A.
Pieniazek
,
Y. M.
Rhee
,
J.
Ritchie
,
E.
Rosta
,
C. D.
Sherrill
,
A. C.
Simmonett
,
J. E.
Subotnik
,
H. L.
Woodcock
 III
,
W.
Zhang
,
A. T.
Bell
,
A. K.
Chakraborty
,
D. M.
Chipman
,
F. J.
Keil
,
A.
Warshel
,
W. J.
Hehre
,
H. F.
Schaefer
 III
,
J.
Kong
,
A. I.
Krylov
,
P. M. W.
Gill
, and
M.
Head-Gordon
,
Phys. Chem. Chem. Phys.
8
,
3172
(
2006
).
27.
O. A.
Vydrov
,
Q.
Wu
, and
T.
Van Voorhis
,
J. Chem. Phys.
129
,
014106
(
2008
).
28.
J. P.
Perdew
and
Y.
Wang
,
Phys. Rev. B
45
,
13244
(
1992
).
29.
R.
Podeszwa
,
K.
Patkowski
, and
K.
Szalewicz
,
Phys. Chem. Chem. Phys.
12
,
5974
(
2010
).
30.
T.
Takatani
,
E. G.
Hohenstein
,
M.
Malagoli
,
M. S.
Marshall
, and
C. D.
Sherrill
,
J. Chem. Phys.
132
,
144104
(
2010
).
31.
K. T.
Tang
and
J. P.
Toennies
,
J. Chem. Phys.
118
,
4976
(
2003
).
32.
C. D.
Sherrill
,
T.
Takatani
, and
E. G.
Hohenstein
,
J. Phys. Chem. A
113
,
10146
(
2009
).
33.
F.
Jensen
,
J. Chem. Phys.
116
,
7372
(
2002
);
F.
Jensen
,
J. Chem. Phys.
117
,
9234
(
2002
);
F.
Jensen
,
J. Phys. Chem. A
111
,
11198
(
2007
);
[PubMed]
F.
Jensen
and
T.
Helgaker
,
J. Chem. Phys.
121
,
3463
(
2004
).
[PubMed]
34.
E. R.
Davidson
,
S. A.
Hagstrom
,
S. J.
Chakravorty
,
V. M.
Umar
, and
C.
Froese Fischer
,
Phys. Rev. A
44
,
7071
(
1991
).
35.
S. J.
Chakravorty
,
S. R.
Gwaltney
,
E. R.
Davidson
,
F. A.
Parpia
, and
C.
Froese Fischer
,
Phys. Rev. A
47
,
3649
(
1993
).
36.
B. J.
Lynch
and
D. G.
Truhlar
,
J. Phys. Chem. A
107
,
8996
(
2003
).
37.
CRC Handbook of Chemistry and Physics
, ed., edited by
D. R.
Lide
(
CRC Press
,
Boca Raton, FL
,
2009
)
38.
O. A.
Vydrov
and
G. E.
Scuseria
,
J. Chem. Phys.
125
,
234109
(
2006
).
39.
O. A.
Vydrov
,
G. E.
Scuseria
, and
J. P.
Perdew
,
J. Chem. Phys.
126
,
154109
(
2007
).
40.
T.
Sato
,
T.
Tsuneda
, and
K.
Hirao
,
J. Chem. Phys.
126
,
234114
(
2007
).
41.
E.
Weintraub
,
T. M.
Henderson
, and
G. E.
Scuseria
,
J. Chem. Theory Comput.
5
,
754
(
2009
).
42.
K.
Pernal
,
R.
Podeszwa
,
K.
Patkowski
, and
K.
Szalewicz
,
Phys. Rev. Lett.
103
,
263201
(
2009
).
43.
J.
Klimeš
,
D. R.
Bowler
, and
A.
Michaelides
,
J. Phys.: Condens. Matter
22
,
022201
(
2010
).
44.
V. R.
Cooper
,
Phys. Rev. B
81
,
161104
(
2010
).
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