In this work, a first-principles systematic study of (Pt3Cu)n, n = 1–9, clusters was performed employing the linear combination of Gaussian-type orbital auxiliary density functional theory approach. The growth of the clusters has been achieved by increasing the previous cluster by one Pt3Cu unit at a time. To explore in detail the potential energy surface of these clusters, initial structures were obtained from Born–Oppenheimer molecular dynamics trajectories generated at different temperatures and spin multiplicities. For each cluster size, several dozens of structures were optimized without any constraints. The most stable structures were characterized by frequency analysis calculations. This study demonstrates that the obtained most stable structures prefer low spin multiplicities. To gain insight into the growing pattern of these systems, average bond lengths were calculated for the lowest stable structures. This work reveals that the Cu atoms prefer to be together and to localize inside the cluster structures. Moreover, these systems tend to form octahedra moieties in the size range of n going from 4 to 9 Pt3Cu units. Magnetic moment per atom and spin density plots were obtained for the neutral, cationic, and anionic ground state structures. Dissociation energies, ionization potential, and electron affinity were calculated, too. The dissociation energy and the electron affinity increase as the number of Pt3Cu units grows, whereas the ionization potential decreases.

1.
A. W.
Castleman
, Jr.
and
R. G.
Keesee
,
Annu. Rev. Phys. Chem.
37
,
525
(
1986
).
2.
L. D.
Pachón
and
G.
Rothenberg
,
Appl. Organomet. Chem.
22
,
288
(
2008
).
3.
E.
Roduner
,
Nanoscopic Materials Size-Dependent Phenomena
(
RSC Publishing
,
Cambridge
,
2006
).
4.
J.
Wu
and
H.
Yang
,
Acc. Chem. Res.
46
(
8
),
1848
(
2013
).
5.
Z. W.
Seh
,
J.
Kibsgaard
,
C. F.
Dickens
,
I.
Chorkendorff
,
J. K.
Nørskov
, and
T. F.
Jaramillo
,
Science
355
,
eaad4998
(
2017
).
6.
H.
Cruz-Martínez
,
M. M.
Tellez-Cruz
,
O. X.
Guerrero-Gutiérrez
,
C. A.
Ramírez-Herrera
,
M. G.
Salinas-Juárez
,
A.
Velázquez-Osorios
, and
O.
Solorza-Feria
,
Int. J. Hydrogen Energy
44
(
24
),
12477
(
2019
).
7.
X.
Wang
,
Z.
Li
,
Y.
Qu
,
T.
Yuan
,
W.
Wang
,
Y.
Wus
, and
Y.
Li
,
Chem
5
,
1486
(
2019
).
8.
A.
Mahata
,
A. S.
Nair
, and
B.
Pathak
,
Catal. Sci. Technol.
9
,
4835
(
2019
).
9.
M.
Oezaslan
,
F.
Haschés
, and
P.
Strasser
,
J. Electrochem. Soc.
159
(
4
),
B444
(
2012
).
10.
X.
Sun
,
K.
Jiang
,
N.
Zhang
,
S.
Guo
, and
X.
Huang
,
ACS Nano
9
(
7
),
7634
(
2015
).
11.
Y.
Kuang
,
Z.
Cai
,
Y.
Zhang
,
D.
He
,
X.
Yan
,
Y.
Bi
,
Y.
Li
,
Z.
Li
, and
X.
Sun
,
ACS Appl. Mater. Interfaces
6
,
17748
(
2014
).
12.
Z.
Wu
,
D.
Dang
, and
X.
Tian
,
ACS Appl. Mater. Interfaces
11
,
9117
(
2019
).
13.
A. S.
Chaves
,
G. G.
Rondina
,
M. J.
Piotrowski
, and
J. L. F.
Da Silva
,
Comput. Mater. Sci.
98
,
278
(
2015
).
14.
A. S.
Chaves
,
M. J.
Piotrowski
,
D.
Guedes-Sobrinho
, and
J. L. F.
Da Silva
,
J. Phys. Chem. A
119
,
11565
(
2015
).
15.
D.
Guedes-Sobrinho
,
R. K.
Nomiyama
,
A. S.
Chaves
,
M. J.
Piotrowski
, and
J. L. F.
Da Silva
,
J. Phys. Chem. C
119
,
15669
(
2015
).
16.
N.
Takagi
,
K.
Ishimura
,
M.
Matsui
,
R.
Fukuda
,
M.
Ehara
, and
S.
Sakaki
,
J. Phys. Chem. C
121
,
10514
(
2017
).
17.
L. E.
Gálvez-González
,
J. O.
Juárez-Sánchez
,
R.
Pacheco-Contreras
,
I. L.
Garzón
,
L. O.
Paz-Borbón
, and
A.
Posada-Amarillas
,
Phys. Chem. Chem. Phys.
20
,
17071
(
2018
).
18.
L. O.
Paz-Borbón
,
F.
Buendía
,
I. L.
Garzón
,
A.
Posada-Amarillas
,
F.
Illas
, and
J.
Li
,
Phys. Chem. Chem. Phys.
21
,
15286
(
2019
).
19.
A. S.
Nair
and
B.
Pathak
,
J. Phys. Chem. C
123
,
3634
(
2019
).
20.
E.
Flores-Rojas
,
H.
Cruz-Martínez
,
H.
Rojas-Chávez
,
M. M.
Tellez-Cruz
,
J. L.
Reyes-Rodríguez
,
J. G.
Cabañas-Moreno
,
P.
Calaminici
, and
O.
Solorza-Feria
,
Electrocatalysis
9
,
662
(
2018
).
21.
S.
Noh
,
J.
Hwang
,
J.
Kang
, and
B.
Han
,
Curr. Opin. Electrochem.
12
,
225
232
(
2018
).
22.
J. M.
Lee
,
H.
Han
,
S.
Jin
,
S. M.
Choi
,
H. J.
Kim
,
M. H.
Seo
, and
W. B.
Kim
,
Energy Technol.
7
,
1900312
(
2019
).
23.
P.
Calaminici
,
Chem. Phys. Lett.
387
,
253
(
2004
).
24.
P.
Calaminici
,
A. M.
Köster
, and
Z.
Gómez-Sandoval
,
J. Chem. Theory Comput.
3
,
905
(
2007
).
25.
G.
López Arvizu
and
P.
Calaminici
,
J. Chem. Phys.
126
,
194102
(
2007
).
26.
P.
Calaminici
,
J. Chem. Phys.
128
,
164317
(
2008
).
27.
P.
Calaminici
and
R.
Mejia-Olvera
,
J. Phys. Chem. C
115
,
11891
(
2011
).
28.
A. M.
Köster
,
P.
Calaminici
,
E.
Orgaz
,
R.
Debesh
,
J. U.
Reveles
, and
S. N.
Khanna
,
J. Am. Chem. Soc.
133
,
12192
(
2011
).
29.
J. U.
Reveles
,
A. M.
Köster
,
P.
Calaminici
, and
S. N.
Khanna
,
J. Chem. Phys.
136
,
114505
(
2012
).
30.
P.
Calaminici
,
J. M.
Vásquez-Pérez
, and
D. A.
Espíndola Velasco
,
Can. J. Chem.
91
,
591
(
2013
).
31.
P.
Calaminici
,
M.
Pérez-Romero
,
J. M.
Vásquez-Pérez
, and
A. M.
Köster
,
Comput. Theor. Chem.
1021
,
41
(
2013
).
32.
V. M.
Medel
,
A. C.
Reber
,
V.
Chauhan
,
P.
Sen
,
A. M.
Köster
,
P.
Calaminici
, and
S. N.
Khanna
,
J. Am. Chem. Soc.
136
,
8229
(
2014
).
33.
W. H.
Blades
,
A. C.
Reber
,
S. N.
Khanna
,
L.
López-Sosa
,
P.
Calaminici
, and
A. M.
Köster
,
J. Phys. Chem. A
121
,
2990
(
2017
).
34.
H.
Cruz-Martínez
,
J. M.
Vásquez-Pérez
,
O.
Solorza-Feria
, and
P.
Calaminici
, “
On the ground state structures and energy properties of ConPdn (n = 1–10) clusters
,” in
Advances in Quantum Chemistry: Concepts of Mathematical Physics in Chemistry: A Tribute to Frank E. Harris
, edited by
J. R.
Sabin
and
R.
Cabrera-Trujillo
(
Elsevier
,
2016
), Vol. 72, Chap. 7, pp.
177
199
.
35.
H.
Cruz-Martínez
,
E.
Flores-Rojas
,
M. M.
Tellez-Cruz
,
J. F.
Pérez-Robles
,
M. A.
Leyva-Ramírez
,
P.
Calaminici
, and
O.
Solorza-Feria
,
Int. J. Hydrogen Energy
41
,
23301
(
2016
).
36.
A.
Cervantes-Flores
,
H.
Cruz-Martínez
,
O.
Solorza-Feria
, and
P.
Calaminici
,
J. Mol. Model.
23
,
161
(
2017
).
37.
H.
Cruz-Martínez
,
M. M.
Tellez-Cruz
,
H.
Rojas-Chávez
,
C. A.
Ramírez-Herrera
,
P.
Calaminici
, and
O.
Solorza-Feria
,
Int. J. Hydrogen Energy
44
,
12463
(
2019
).
38.
L.
López-Sosa
,
H.
Cruz-Martínez
,
O.
Solorza-Feria
, and
P.
Calaminici
,
Int. J. Quantum Chem.
119
,
e26013
(
2019
).
39.
H.
Cruz-Martínez
,
O.
Solorza-Feria
,
P.
Calaminici
, and
D. I.
Medina
,
J. Magn. Magn. Mater.
508
,
166844
(
2020
).
40.
A. M.
Köster
,
J. U.
Reveles
, and
J. M.
del Campo
,
J. Chem. Phys.
121
,
3417
(
2004
).
41.
G.
Geudtner
,
P.
Calaminici
,
J.
Carmona-Espíndola
,
J. M.
del Campo
,
V. D.
Domínguez-Soria
,
R. F.
Moreno
,
G. U.
Gamboa
,
A.
Goursot
,
A. M.
Köster
,
J. U.
Reveles
,
T.
Mineva
,
J. M.
Vásquez-Pérez
,
A.
Vela
,
B.
Zúñinga-Gutierrez
, and
D. R.
Salahub
, “
deMon2k
,”
Wiley Interdiscip. Rev.: Comput. Mol. Sci.
2
,
548
(
2012
).
42.
A. M.
Köster
,
G.
Geudtner
,
A.
Alvarez-Ibarra
,
P.
Calaminici
,
M. E.
Casida
,
J.
Carmona-Espindola
,
V. D.
Dominguez
,
R.
Flores-Moreno
,
G. U.
Gamboa
,
A.
Goursot
,
T.
Heine
,
A.
Ipatov
,
A.
de la Lande
,
F.
Janetzko
,
J. M.
del Campo
,
D.
Mejia-Rodriguez
,
J. U.
Reveles
,
J.
Vasquez-Perez
,
A.
Vela
,
B.
Zuniga-Gutierrez
, and
D. R.
Salahub
, deMon2k, Version 6, The deMon developers,
Cinvestav
,
Mexico City
,
2018
.
43.
M.
Krack
and
A. M.
Köster
,
J. Chem. Phys.
108
,
3226
(
1998
).
44.
J. W.
Mintmire
and
B. I.
Dunlap
,
Phys. Rev. A
25
,
88
(
1982
).
45.
Y.
Zhang
and
W.
Yang
,
Phys. Rev. Lett.
80
,
890
(
1999
).
46.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
,
3865
(
1996
).
47.
P.
Calaminici
,
F.
Janetzko
,
A. M.
Köster
,
R.
Mejia-Olvera
, and
B.
Zuniga-Gutierrez
,
J. Chem. Phys.
126
,
044108
(
2007
).
48.
P. J.
Hay
and
W. R.
Wadt
,
J. Chem. Phys.
82
,
270
(
1985
).
49.
P.
Calaminici
,
A.
Alvarez-Ibarra
,
D.
Cruz-Olvera
,
V.
Dominguez-Soria
,
R.
Flores-Moreno
,
G. U.
Gamboa
,
G.
Geudtner
,
A.
Goursot
,
D.
Mejia-Rodriguez
,
D. R.
Salahub
,
B.
Zuniga-Gutierrez
, and
A. M.
Köster
, “
Auxiliary density functional theory: From molecules to nanostructures
,” in
Handbook of Computational Chemistry
, edited by
J.
Leszczynski
,
A.
Kaczmarek-Kedziera
,
T.
Puzyn
,
M. G.
Papadopoulos
,
H.
Reis
, and
M. K.
Shukla
(
Springer
,
Cham
,
2017
).
50.
S.
Nosé
,
J. Chem. Phys.
81
,
511
(
1984
).
51.
G. J.
Martyna
,
M. L.
Klein
, and
M.
Tuckerman
,
J. Chem. Phys.
97
,
2635
(
1992
).
52.
J. M.
Vásquez-Pérez
,
G. U. G.
Martínez
,
A. M.
Köster
, and
P.
Calaminici
,
J. Chem. Phys.
131
,
124126
(
2009
).
53.
R. I.
Delgado-Venegas
,
D.
Mejía-Rodríguez
,
R.
Flores-Moreno
,
P.
Calaminici
, and
A. M.
Köster
,
J. Chem. Phys.
145
,
224103
(
2016
).
54.
W.
Humphrey
,
A.
Dalke
, and
K.
Schulten
,
J. Mol. Graphics
14
,
33
(
1996
).
55.
K. L.
Schuchardt
,
B. T.
Didier
,
T.
Elsethagen
,
L.
Sun
,
V.
Gurumoorthi
,
J.
Chase
,
J.
Li
, and
T. L.
Windus
,
J. Chem. Inf. Model.
47
,
1045
(
2007
).
56.
L. S. C.
Martins
,
F. E.
Jorge
, and
S. F.
Machado
,
Mol. Phys.
113
,
3578
(
2015
).
57.
J.
Ho
,
M. L.
Polak
,
K. M.
Ervin
, and
W. C.
Lineberger
,
J. Chem. Phys.
99
,
8542
(
1993
).
58.
E. M.
Spain
and
M. D.
Morse
,
J. Chem. Phys.
97
,
4605
(
1992
).
59.
D. G.
Leopold
,
J.
Ho
, and
W. C.
Lineberger
,
J. Chem. Phys.
86
,
1715
(
1988
).
60.
M. B.
Airola
and
M. D.
Morse
,
J. Chem. Phys.
116
,
1313
(
2002
).
61.
S.
Taylor
,
G. W.
Lemire
,
Y. M.
Hamrick
,
Z.
Fu
, and
M. D.
Morse
,
J. Chem. Phys.
89
,
5517
(
1988
).
62.
J. C.
Fabbi
,
L.
Karlsson
,
J. D.
Langenberg
,
Q. D.
Costello
, and
M. D.
Morse
,
J. Chem. Phys.
118
,
9247
(
2003
).
63.
A.
Köhn
,
F.
Weigend
, and
R.
Ahlrichs
,
Phys. Chem. Chem. Phys.
3
,
711
(
2001
).
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