Local density of states and electric charge in regions defined for individual atoms and molecules using grid based Bader analysis is presented for N2 and CO2 adsorbed on a platinum electrode in the presence of an applied electric field. When the density of states is projected onto Bader regions, the partial density of states for the various subregions correctly sums up to the total density of states for the whole system, unlike the commonly used projection onto spheres which results in missing contributions from some regions while others are over counted, depending on the radius chosen. The electrode is represented by a slab with a missing row reconstructed Pt(110)-(1 × 2) surface to model an edge between micro-facets on the surface of a nano-particle catalyst. For both N2 and CO2, a certain electric field window leads to adsorption. The binding of N2 to the electrode is mainly due to polarization of the molecule but for CO2 hybridization occurs between the molecular states and the states of the Pt electrode.

1.
J. S.
Filhol
and
M.
Neurock
,
Angew. Chem., Int. Ed.
45
,
402
(
2006
).
2.
M.
Otani
and
O.
Sugino
,
Phys. Rev. B
73
,
115407
(
2006
).
3.
R.
Jinnouchi
and
A. B.
Anderson
,
J. Phys. Chem. C
112
,
8747
(
2008
).
4.
E.
Skúlason
,
G. S.
Karlberg
,
J.
Rossmeisl
,
T.
Bligaard
,
J.
Greeley
,
H.
Jónsson
, and
J. K.
Nørskov
,
Phys. Chem. Chem. Phys.
9
,
3241
(
2007
).
5.
J.
Rossmeisl
,
E.
Skúlason
,
M. E.
Björketun
,
V.
Tripkovic
, and
J. K.
Nørskov
,
Chem. Phys. Lett.
466
,
68
(
2008
).
6.
V.
Tripkovic
,
E.
Skúlason
,
S.
Siahrostami
,
J. K.
Nørskov
, and
J.
Rossmeisl
,
Electrochim. Acta
55
,
7975
(
2010
).
7.
E.
Skúlason
,
V.
Tripkovic
,
M. E.
Björketun
,
S.
Gudmundsdóttir
,
G.
Karlberg
,
J.
Rossmeisl
,
T.
Bligaard
,
H.
Jónsson
, and
J. K.
Nørskov
,
J. Phys. Chem. C
114
,
18182
(
2010
).
8.
V.
Tripkovic
,
M. E.
Björketun
,
E.
Skúlason
, and
J.
Rossmeisl
,
Phys. Rev. B
84
,
115452
(
2011
).
9.
M. E.
Björketun
,
V.
Tripkovic
,
E.
Skúlason
, and
J.
Rossmeisl
, “
Modeling of the symmetry factor of electrochemical proton discharge via the Volmer reaction
,”
Catal. Today
(in press).
10.
J. K.
Nørskov
,
J.
Rossmeisl
,
A.
Logadottir
,
L.
Lindqvist
,
J. R.
Kitchin
,
T.
Bligaard
, and
H.
Jónsson
,
J. Phys. Chem. B
108
,
17886
(
2004
).
11.
A.
Roudgar
and
A.
Gross
,
Chem. Phys. Lett.
409
,
157
(
2005
).
12.
J.
Rossmeisl
,
J. K.
Nørskov
,
C.
Taylor
,
M.
Janik
, and
M.
Neurock
,
J. Phys. Chem. B
110
,
21833
(
2006
).
13.
G. S.
Karlberg
,
J.
Rossmeisl
, and
J. K.
Nørskov
,
Phys. Chem. Chem. Phys.
9
,
5158
(
2007
).
14.
G. S.
Karlberg
,
T. F.
Jaramillo
,
E.
Skúlason
,
J.
Rossmeisl
,
T.
Bligaard
, and
J. K.
Nørskov
,
Phys. Rev. Lett.
99
,
126101
(
2007
).
15.
E.
Skúlason
,
T.
Bligaard
,
S.
Gudmundsdóttir
,
F.
Studt
,
J.
Rossmeisl
,
F.
Abild-Pedersen
,
T.
Vegge
,
H.
Jónsson
, and
J.
Nørskov
,
Phys. Chem. Chem. Phys.
14
,
1235
(
2012
).
16.
A.
Hellman
 et al,
J. Phys. Chem. B
110
,
17719
(
2006
).
17.
W.
An
and
C. H.
Turner
,
Chem. Phys. Lett.
482
,
247
(
2009
).
18.
C.-C.
Wang
,
S. S.
Siao
, and
J.-C.
Jiang
,
J. Phys. Chem. C
114
,
18588
(
2010
).
19.
J.
Gavnholt
,
T.
Olsen
,
M.
Engelund
, and
J.
Schiøtz
,
Phys. Rev. B
78
,
075441
(
2008
).
20.
S.-G.
Wang
,
X.-Y.
Liao
,
D.-B.
Cao
,
C.-F.
Huo
,
Y.-W.
Li
,
J.
Wang
, and
H.
Jiao
,
J. Phys. Chem. C
111
,
16934
(
2007
).
21.
Y.
Liu
and
J.
Wilcox
,
Environ. Sci. Technol.
45
,
809
(
2011
).
22.
J. D.
Baniecki
,
M.
Ishii
,
K.
Kurihara
,
K.
Yamanaka
,
T.
Yano
,
K.
Shinozaki
,
T.
Imada
,
K.
Nozaki
, and
N.
Kin
,
Phys. Rev. B
78
,
195415
(
2008
).
23.
Y.
Duan
and
D. C.
Sorescu
,
Phys. Rev. B
79
,
014301
(
2009
).
24.
A. A.
Peterson
,
F.
Abild-Pedersen
,
F.
Studt
,
J.
Rossmeisl
, and
J.
Nørskov
,
Energy Environ. Sci.
3
,
1311
(
2010
).
25.
R.
Bader
,
Atoms in Molecules: A Quantum Theory
(
Oxford University Press
,
New York
,
1990
).
26.
P. L. A.
Popelier
, MORPHY98, a program written by Popelier with a contribution from R. G. A. Bone, UMIST, Manchester, England,
1998
.
27.
B. B.
Stefanov
and
J.
Cioslowski
,
J. Comput. Chem.
16
,
1394
(
1995
).
28.
P. L. A.
Popelier
,
Theor. Chem. Acc.
105
,
393
(
2001
).
29.
P. L. A.
Popelier
,
Theor. Chim. Acta
87
,
465
(
1994
).
30.
P. L. A.
Popelier
,
Comput. Phys. Commun.
108
,
180
(
1998
).
31.
N. O. J.
Malcolm
and
P. L. A.
Popelier
,
J. Comput. Chem.
24
,
437
(
2003
);
[PubMed]
N. O. J.
Malcolm
and
P. L. A.
Popelier
,
J. Comput. Chem.
24
,
1276
(
2003
).
[PubMed]
32.
B. P.
Uberuaga
,
E. R.
Batista
, and
H.
Jónsson
,
J. Chem. Phys.
111
,
10664
(
1999
).
33.
F. W.
Biegler-König
,
J.
Schönbohm
, and
D.
Bayles
,
J. Comput. Chem.
22
,
545
559
(
2001
).
34.
G.
Henkelman
,
A.
Arnaldsson
, and
H.
Jónsson
,
Comput. Mater. Sci.
36
,
354
(
2006
).
35.
E.
Sanville
,
S. D.
Kenny
,
R.
Smith
, and
G.
Henkelman
,
J. Comput. Chem.
28
,
899
(
2007
).
36.
W.
Tang
,
E.
Sanville
, and
G.
Henkelman
,
J. Phys.: Condens. Matter
21
,
084204
(
2009
).
37.
M.
Yu
and
D. R.
Trinkle
,
J. Chem. Phys.
134
,
064111
(
2011
).
38.
See http://theory.cm.utexas.edu/bader/ for grid based Bader charge analysis.
39.
S.
Gudmundsdóttir
,
E.
Skúlason
, and
H.
Jónsson
,
Phys. Rev. Lett.
108
,
156101
(
2012
).
40.
S.
Gudmundsdóttir
,
E.
Skúlason
,
K.-J.
Weststrate
,
L.
Juurlink
, and
H.
Jonsson
, “
Hydrogen adsorption and desorption at the Pt(110)-(1×2) surface: Experimental and theoretical study
,” Phys. Chem. Chem. Phys. (submitted).
41.
G.
Kresse
and
J.
Hafner
,
Phys. Rev. B
47
,
558
(
1993
).
42.
G.
Kresse
and
J.
Hafner
,
Phys. Rev. B
49
,
14251
(
1994
).
43.
G.
Kresse
and
J.
Furthmüller
,
Comput. Mater. Sci.
6
,
16
(
1996
).
44.
See http://theory.cm.utexas.edu/vtsttools/dos/ for .DOS projection in Bader volumes.
45.
46.
See https://wiki.fysik.dtu.dk/dacapo for Dacapo pseudopotential code, Center for Atomic-scale Materials Design (CAMD), Technical University of Denmark, Lyngby.
47.
B.
Hammer
,
L. B.
Hansen
, and
J. K.
Nørskov
,
Phys. Rev. B
46
,
7413
(
1999
).
48.
P. E.
Blöchl
,
Phys. Rev. B
50
,
17953
(
1994
).
49.
50.
B.
Hammer
and
J. K.
Nørskov
,
Surf. Sci.
343
,
211
(
1995
).
51.
J. K.
Nørskov
, private communication (2010–2011).
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