With a simple and physically intuitive method, first-principles calculations of potential-energy surfaces are performed for excited states in a number of illustrative systems, including dimers (H2 and NaCl) and gas–surface systems [Cl–Na(100) and Cl2Na(100)]. It is based on density-functional theory and is a generalization of the Δ self-consistent field (ΔSCF) method, where electron–hole pairs are introduced in order to model excited states, corresponding to internal electron transfers in the considered system. The desired excitations are identified by analysis of calculated electron orbitals, local densities of states, and charge densities. For extended systems, where reliable first-principles methods to account for electronically excited states have so far been scarce, our method is very promising. Calculated results, such as the chemiluminescence of halogen molecules impinging on a alkali–metal surface, and the vertical (5σ→2π*) excitation within the adsorbed CO molecule on the Pd(111) surface, are in working agreement with those of other studies and experiments.

1.
P.
Hohenberg
and
W.
Kohn
,
Phys. Rev.
136
,
B864
(
1964
).
2.
W.
Kohn
and
L. J.
Sham
,
Phys. Rev.
140
,
A1133
(
1965
).
3.
S.
Kurth
,
J. P.
Perdew
, and
P.
Blaha
,
Int. J. Quantum Chem.
75
,
889
(
1999
).
4.
M.
Born
and
R.
Oppenheimer
,
Ann. Phys. (Leipzig)
84
,
457
(
1927
).
5.
F. T.
Smith
,
Phys. Rev.
179
,
111
(
1969
).
6.
T. F.
O’Malley
,
Adv. At. Mol. Phys.
7
,
223
(
1971
).
7.
T.
Greber
,
Surf. Sci. Rep.
28
,
1
(
1997
).
8.
H.
Nienhaus
,
Surf. Sci. Rep.
45
,
1
(
2002
).
9.
T. S.
Rose
,
M. J.
Rosker
, and
A. H.
Zewail
,
J. Chem. Phys.
91
,
7415
(
1989
).
10.
J. K.
Nørskov
,
D. M.
Newns
, and
B. I.
Lundqvist
,
Surf. Sci.
80
,
179
(
1979
).
11.
L.
Hellberg
,
J.
Strömquist
,
B.
Kasemo
, and
B. I.
Lundqvist
,
Phys. Rev. Lett.
74
,
4742
(
1995
).
12.
J.
Strömquist
,
L.
Hellberg
,
B.
Kasemo
, and
B. I.
Lundqvist
,
Surf. Sci.
352–354
,
435
(
1996
).
13.
L.
Österlund
,
I.
Zorić
, and
B.
Kasemo
,
Phys. Rev. B
55
,
15452
(
1997
).
14.
K.
Honkala
and
K.
Laasonen
,
Phys. Rev. Lett.
84
,
705
(
2000
).
15.
Y.
Yourdshahyan
,
B.
Razaznejad
, and
B. I.
Lundqvist
,
Solid State Commun.
117
,
531
(
2001
).
16.
Y.
Yourdshahyan
,
B.
Razaznejad
, and
B. I.
Lundqvist
,
Phys. Rev. B
65
,
075416
(
2002
).
17.
A.
Hellman
,
B.
Razaznejad
,
Y.
Yourdshahyan
,
H.
Ternow
,
I.
Zorić
, and
B. I.
Lundqvist
,
Surf. Sci.
532–535
,
126
(
2003
).
18.
J. K.
Nørskov
and
B. I.
Lundqvist
,
Surf. Sci.
80
,
251
(
1979
).
19.
Laser Spectroscopy and Photochemistry on Metal Surfaces, edited by H. L. Dai and W. Ho (World Scientific, Singapore 1995).
20.
A. J.
Komrowski
,
J. Z.
Sexton
,
A. C.
Kummel
,
M.
Binettis
,
O.
Wieße
, and
E.
Hasselbrink
,
Phys. Rev. Lett.
87
,
246103
(
2001
).
21.
L.
Hedin
,
Phys. Rev.
139
,
A796
(
1965
).
22.
M.
Rohlfing
,
Int. J. Quantum Chem.
91
,
7415
(
1989
).
23.
G.
Onida
,
L.
Reining
, and
A.
Rubio
,
Rev. Mod. Phys.
74
,
601
(
2002
).
24.
A.
Görling
and
M.
Levy
,
Phys. Rev. B
47
,
13105
(
1993
).
25.
A.
Görling
,
Phys. Rev. A
54
,
3912
(
1996
).
26.
C.
Filippi
,
C. J.
Umrigar
, and
X.
Gonze
,
J. Chem. Phys.
107
,
9994
(
1997
).
27.
A.
Zangwill
and
P.
Soven
,
Phys. Rev. A
21
,
1561
(
1980
).
28.
E.
Runge
and
E. K. U.
Gross
,
Phys. Rev. Lett.
52
,
997
(
1984
).
29.
E. K. U.
Gross
and
W.
Kohn
,
Adv. Quantum Chem.
21
,
255
(
1990
).
30.
T.
Klüner
,
N.
Govind
,
Y. A.
Wang
, and
E. A.
Carter
,
J. Chem. Phys.
116
,
42
(
2002
).
31.
O.
Gunnarsson
and
B. I.
Lundqvist
,
Phys. Rev. B
13
,
4274
(
1976
).
32.
R.
Monnier
,
J. P.
Perdew
,
D. C.
Langreth
, and
J. W.
Wilkins
,
Phys. Rev. B
18
,
656
(
1978
).
33.
U.
von Barth
,
Phys. Rev. A
20
,
1693
(
1979
).
34.
R. O.
Jones
and
O.
Gunnarsson
,
Rev. Mod. Phys.
61
,
689
(
1989
).
35.
G.
Gardet
,
F.
Rogemond
, and
H.
Chermette
,
Theor. Chim. Acta
91
,
249
(
1995
).
36.
A.
Görling
,
Phys. Rev. A
59
,
3359
(
1999
).
37.
F.
Aryasetiawan
and
O.
Gunnarson
,
Rep. Prog. Phys.
61
,
237
(
1998
).
38.
J. C.
Grossmann
,
M.
Rohlfing
,
L.
Mitas
,
S. G.
Louie
, and
M. L.
Cohen
,
Phys. Rev. Lett.
86
,
472
(
2001
).
39.
A.
Marini
,
G.
Onida
, and
R. Del
Sole
,
Phys. Rev. Lett.
88
,
016403
(
2002
).
40.
M.
Rohlfing
and
S. G.
Louie
,
Phys. Rev. B
62
,
4927
(
2000
).
41.
M.
Petersilka
,
E. K. U.
Gross
, and
K.
Burke
,
Int. J. Quantum Chem.
80
,
534
(
2000
).
42.
O. V.
Gritsenko
,
S. J. A.
van Gisbergen
,
A.
Görling
, and
E. J.
Baerends
,
J. Chem. Phys.
113
,
8478
(
2000
).
43.
K.
Tatarczyk
,
A.
Schindlmayer
, and
M.
Scheffler
,
Phys. Rev. B
63
,
235106
(
2001
).
44.
M. E.
Casida
,
F.
Gutierrez
,
J.
Guan
,
F.
Gafea
,
D.
Salahub
, and
J.
Daudey
,
J. Chem. Phys.
113
,
7062
(
2000
).
45.
A.
Dreuw
,
J. L.
Weisman
, and
M.
Head-Gordon
,
J. Chem. Phys.
119
,
2943
(
2003
).
46.
J. C.
Slater
,
Phys. Rev.
32
,
339
(
1928
).
47.
T.
Ziegler
,
A.
Rauk
, and
E. J.
Baerends
,
Theor. Chim. Acta
43
,
877
(
1977
).
48.
J. P.
Perdew
,
R. G.
Parr
,
M.
Levy
, and
J. L.
Balduz
, Jr.
,
Phys. Rev. Lett.
49
,
1691
(
1982
).
49.
B. Hammer, “computer code DACAPO-1.30,” Denmark Technical University, Lyngby, Denmark (1999).
50.
J. P.
Perdew
,
J. A.
Chevary
,
S. H.
Vosko
,
K. A.
Jackson
,
M. R.
Pederson
,
D. J.
Singh
, and
C.
Fiolhais
,
Phys. Rev. B
46
,
6671
(
1992
).
51.
J. P. Perdew, in Electronic Structure of Solids, edited by P. Ziesche and H. Eschrig (Akademie Verlag, Berlin, 1991), Vol. 11.
52.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
,
3865
(
1996
).
53.
D.
Vanderbilt
,
Phys. Rev. B
41
,
7892
(
1990
).
54.
G.
Kresse
and
J.
Furtmüller
,
Comput. Mater. Sci.
6
,
15
(
1996
).
55.
H. J.
Monkhorst
and
J. D.
Pack
,
Phys. Rev. B
13
,
5188
(
1976
).
56.
L.
Hedin
and
B. I.
Lundqvist
,
Z. Phys. C
4
,
2064
(
1971
).
57.
L.
Bengtsson
,
Phys. Rev. B
59
,
12301
(
1999
).
58.
W.
Heitler
and
F.
London
,
Z. Phys.
44
,
455
(
1927
).
59.
W.
Kolos
and
L.
Wolniewicz
,
J. Chem. Phys.
43
,
2429
(
1965
).
60.
Z.
Chi
and
J. R.
Reimers
,
J. Chem. Phys.
112
,
527
(
2000
).
61.
Y.
Zeiri
and
G. G.
Balint-Kurti
,
J. Mol. Spectrosc.
99
,
1
(
1983
).
62.
J. A.
Silver
,
D. R.
Worsnop
,
A.
Freedman
, and
C. E.
Kolb
,
J. Chem. Phys.
84
,
4378
(
1986
).
63.
N. D.
Lang
,
J. K.
Nørskov
, and
B. I.
Lundqvist
,
Phys. Scr.
34
,
77
(
1986
).
64.
B.
Kasemo
and
L.
Walldén
,
Surf. Sci.
53
,
393
(
1975
).
65.
P.
Nordlander
,
Phys. Rev. B
46
,
2584
(
1992
).
66.
F. P.
Netzer
and
M. M.
El Gomati
,
Surf. Sci.
124
,
26
(
1983
).
67.
H. J.
Freund
,
R. P.
Messmer
,
W.
Spiess
,
H.
Behner
,
G.
Wedler
, and
C. M.
Kao
,
Phys. Rev. B
33
,
5228
(
1986
).
68.
Ph.
Avouris
and
J. E
Demuth
,
Surf. Sci.
158
,
21
(
1985
).
This content is only available via PDF.
You do not currently have access to this content.