With the concept of scaled-opposite-spin (SOS), a pragmatic semi-empirical approximation has been introduced to the extended algebraic diagrammatic construction scheme of second order (ADC(2)-x) that leads to a significant saving in computational effort. The parameters included were fitted with respect to a benchmark set of electronically excited states in standard organic molecules that include some doubly-excited states, as well. Like the original, unscaled ADC(2)-x scheme it can be used to identify electronically excited states with high double excitation character, however at reduced computational cost. At the same time, it is possible to reduce the overestimation of doubly-excited configurations that is inherent to ADC(2)-x. Additionally, a scheme for the strict variant (ADC(2)-s) was derived directly from SOS-MP2 by application of the intermediate state formalism and compared to an existing version of SOS-ADC(2)-s.

1.
S.
Grimme
,
Rev. Comput. Chem.
20
,
153
(
2004
).
2.
A.
Dreuw
and
M.
Head-Gordon
,
Chem. Rev.
105
,
4009
(
2005
).
3.
M.
Merchán
and
L.
Serrano-Andrés
,
Computational Photochemistry
, edited by
M.
Olivucci
, Theoretical and Computational Chemistry Vol. 16 (
Elsevier
,
Amsterdam
,
2005
), Chap. II.
5.
L.
González
,
D.
Escudero
, and
L.
Serrano-Andrés
,
ChemPhysChem
13
,
28
(
2012
).
6.
E.
Runge
and
E. K. U.
Gross
,
Phys. Rev. Lett.
52
,
997
(
1984
).
7.
F.
Furche
and
D.
Rappoport
,
Computational Photochemistry
, edited by
M.
Olivucci
, Theoretical and Computational Chemistry Vol. 16 (
Elsevier
,
Amsterdam
,
2005
), Chap. III.
8.
J. E.
Del Bene
,
R.
Ditchfield
, and
J. A.
Pople
,
J. Chem. Phys.
55
,
2236
(
1971
).
9.
M.
Head-Gordon
,
R. J.
Rico
,
M.
Oumi
, and
T. J.
Lee
,
Chem. Phys. Lett.
219
,
21
(
1994
).
10.
K.
Andersson
,
P. A.
Malmqvist
,
B. O.
Roos
,
A. J.
Sadlej
, and
K.
Wolinski
,
J. Phys. Chem.
94
,
5483
(
1990
).
11.
K.
Andersson
,
P.-A.
Malmqvist
, and
B. O.
Roos
,
J. Chem. Phys.
96
,
1218
(
1992
).
12.
O.
Christiansen
,
H.
Koch
, and
P.
Jørgensen
,
Chem. Phys. Lett.
243
,
409
(
1995
).
13.
C.
Hättig
and
F.
Weigend
,
J. Chem. Phys.
113
,
5154
(
2000
).
14.
S.
Grimme
and
M.
Waletzke
,
J. Chem. Phys.
111
,
5645
(
1999
).
15.
J.
Schirmer
,
Phys. Rev. A
26
,
2395
(
1982
).
16.
J.
Schirmer
and
A. B.
Trofimov
,
J. Chem. Phys.
120
,
11449
(
2004
).
17.
A. B.
Trofimov
,
G.
Stelter
, and
J.
Schirmer
,
J. Chem. Phys.
111
,
9982
(
1999
).
18.
A. B.
Trofimov
and
J.
Schirmer
,
J. Phys. B
28
,
2299
(
1995
).
19.
A. B.
Trofimov
,
G.
Stelter
, and
J.
Schirmer
,
J. Chem. Phys.
117
,
6402
(
2002
).
20.
C.
Møller
and
M. S.
Plesset
,
Phys. Rev.
46
,
618
(
1934
).
21.
J. H.
Starcke
,
M.
Wormit
,
J.
Schirmer
, and
A.
Dreuw
,
Chem. Phys.
329
,
39
(
2006
).
22.
S.
Grimme
,
J. Chem. Phys.
118
,
9095
(
2003
).
23.
R. F.
Fink
,
J. Chem. Phys.
133
,
174113
(
2010
).
24.
S.
Grimme
,
L.
Goerigk
, and
R. F.
Fink
,
WIREs Comput. Mol. Sci.
2
,
886
(
2012
).
25.
Y.
Jung
,
R. C.
Lochan
,
A. D.
Dutoi
, and
M.
Head-Gordon
,
J. Chem. Phys.
121
,
9793
(
2004
).
26.
M.
Feyereisen
,
G.
Fitzgerald
, and
A.
Komornicki
,
Chem. Phys. Lett.
208
,
359
(
1993
).
27.
F.
Weigend
,
M.
Häser
,
H.
Patzelt
, and
R.
Ahlrichs
,
Chem. Phys. Lett.
294
,
143
(
1998
).
28.
J.
Almlöf
,
Chem. Phys. Lett.
181
,
319
(
1991
).
29.
S.
Grimme
and
I.
Izgorodina
,
Chem. Phys.
305
,
223
(
2004
).
30.
Y. M.
Rhee
and
M.
Head-Gordon
,
J. Chem. Phys. A
111
,
5314
(
2007
).
31.
D.
Casanova
,
Y. M.
Rhee
, and
M.
Head-Gordon
,
J. Chem. Phys.
128
,
164106
(
2008
).
32.
Y. M.
Rhee
,
D.
Casanova
, and
M.
Head-Gordon
,
J. Chem. Theory Comput.
5
,
1224
(
2009
).
33.
Y. M.
Rhee
,
D.
Casanova
, and
M.
Head-Gordon
,
J. Phys. Chem. A
113
,
10564
(
2009
).
34.
M.
Head-Gordon
,
M.
Oumi
, and
D.
Maurice
,
Mol. Phys.
96
,
593
(
1999
).
35.
Y.
Shao
,
L. F.
Molnar
,
Y.
Jung
,
J.
Kussmann
,
C.
Ochsenfeld
,
S. T.
Brown
,
A. T.
Gilbert
,
L. V.
Slipchenko
,
S. V.
Levchenko
,
D. P.
O’Neill
,
R. A.
DiStasio
 Jr.
,
R. C.
Lochan
,
T.
Wang
,
G. J.
Beran
,
N. A.
Besley
,
J. M.
Herbert
,
C.
Yeh Lin
,
T.
Van Voorhis
,
S.
Hung 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.
Min Rhee
,
J.
Ritchie
,
E.
Rosta
,
C.
David Sherrill
,
A. C.
Simmonett
,
J. E.
Subotnik
,
H.
Lee 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
).
36.
A.
Hellweg
,
S. A.
Grün
, and
C.
Hättig
,
Phys. Chem. Chem. Phys.
10
,
4119
(
2008
).
37.
TURBOMOLE, a development of the University of Karlsruhe and ForschungszentrumKarlsruhe GmbH, 1989–2007, TURBOMOLE GmbH since 2007, see http://www.turbomole.com.
38.
N. O. C.
Winter
and
C.
Hättig
,
J. Chem. Phys.
134
,
184101
(
2011
).
39.
M.
Schreiber
,
M. R.
Silva-Junior
,
S. P. A.
Sauer
, and
W.
Thiel
,
J. Chem. Phys.
128
,
134110
(
2008
).
40.
C.
Hättig
,
Adv. Quantum Chem.
50
,
37
(
2005
).
41.
See supplementary material at http://dx.doi.org/10.1063/1.4776675 for explicit expressions for the different ADC matrices and documentation of our results with the strict and extended ADC(2) schemes presented in this work.
42.
Y.
Jung
,
A.
Sodt
,
P. M. W.
Gill
, and
M.
Head-Gordon
,
Proc. Natl. Acad. Sci. U.S.A.
102
,
6692
(
2005
).
43.
M. R.
Silva-Junior
,
M.
Schreiber
,
S. P. A.
Sauer
, and
W.
Thiel
,
J. Chem. Phys.
133
,
174318
(
2010
).
44.
T. H.
Dunning
,
J. Chem. Phys.
90
,
1007
(
1989
).
45.
F.
Weigend
,
A.
Köhn
, and
C.
Hättig
,
J. Chem. Phys.
116
,
3175
(
2002
).
46.
M. R.
Silva-Junior
,
M.
Schreiber
,
S. P. A.
Sauer
, and
W.
Thiel
,
J. Chem. Phys.
129
,
104103
(
2008
).
47.
bwGRiD (http://www.bw-grid.de), member of the German D-Grid initiative, funded by the Ministry for Education and Research (Bundesministerium für Bildung und Forschung) and the Ministry for Science, Research and Arts Baden-Württemberg (Ministerium für Wissenschaft, Forschung und Kunst Baden-Württemberg).

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