We study the nucleation of nearly hard charged colloidal particles. We use Monte Carlo simulations in combination with free-energy calculations to accurately predict the phase diagrams of these particles and map them via the freezing density to hard spheres, then we use umbrella sampling to explore the nucleation process. Surprisingly, we find that even very small amounts of charge repulsion can have a significant effect on the phase behavior. Specifically, we find that phase boundaries and nucleation barriers are mostly dependent on the Debye screening length and that even screening lengths as small as 2% of the particle diameter are sufficient to show marked differences in both. This work demonstrates clearly that even mildly charged colloids are not effectively hard spheres.

1.
J. L.
Harland
and
W.
Van Megen
,
Phys. Rev. E
55
,
3054
(
1997
).
2.
U.
Gasser
,
E. R.
Weeks
,
A.
Schofield
,
P. N.
Pusey
, and
D. A.
Weitz
,
Science
292
,
258
(
2001
).
3.
S.
Auer
and
D.
Frenkel
,
Nature
409
,
1020
(
2001
).
4.
A.
Cacciuto
,
S.
Auer
, and
D.
Frenkel
,
Nature
428
,
404
(
2004
).
5.
S.
Auer
and
D.
Frenkel
,
Phys. Rev. Lett.
91
,
015703
(
2003
).
6.
S.
Iacopini
,
T.
Palberg
, and
H. J.
Schöpe
,
J. Chem. Phys.
130
,
084502
(
2009
).
7.
A. L.
Thorneywork
,
J. L.
Abbott
,
D. G. A. L.
Aarts
, and
R. P. A.
Dullens
,
Phys. Rev. Lett.
118
,
158001
(
2017
).
8.
J. M.
Gordon
,
J. H.
Gibbs
, and
P. D.
Fleming
,
J. Chem. Phys.
65
,
2771
(
1976
).
10.
E.
Zaccarelli
,
S. M.
Liddle
, and
W. C. K.
Poon
,
Soft Matter
11
,
324
(
2015
).
11.
A. L.
Thorneywork
,
R.
Roth
,
D. G. A. L.
Aarts
, and
R. P. A.
Dullens
,
J. Chem. Phys.
140
,
161106
(
2014
).
12.
C. H.
Bennett
and
B. J.
Alder
,
J. Chem. Phys.
54
,
4796
(
1971
).
13.
P. N.
Pusey
,
W.
Van Megen
,
P.
Bartlett
,
B. J.
Ackerson
,
J. G.
Rarity
, and
S. M.
Underwood
,
Phys. Rev. Lett.
63
,
2753
(
1989
).
14.
S.
Pronk
and
D.
Frenkel
,
J. Phys. Chem. B
105
,
6722
(
2001
).
15.
S.
Pronk
and
D.
Frenkel
,
J. Chem. Phys.
110
,
4589
(
1999
).
16.
B.
van der Meer
,
M.
Dijkstra
, and
L.
Filion
,
J. Chem. Phys.
146
,
244905
(
2017
).
17.
C.
Sinn
,
A.
Heymann
,
A.
Stipp
, and
T.
Palberg
, in
Trends Colloid Interface Science
(
Springer
,
2001
), Vol. XV, p.
266
.
18.
K.
Schätzel
and
B. J.
Ackerson
,
Phys. Rev. E
48
,
3766
(
1993
).
19.
S.
Auer
and
D.
Frenkel
,
J. Chem. Phys.
120
,
3015
(
2004
).
20.
S.
Auer
and
D.
Frenkel
,
Adv. Comput. Simul.
173
,
149
(
2005
).
21.
E.
Zaccarelli
,
C.
Valeriani
,
E.
Sanz
,
W. C. K.
Poon
,
M. E.
Cates
, and
P. N.
Pusey
,
Phys. Rev. Lett.
103
,
135704
(
2009
).
22.
L.
Filion
,
M.
Hermes
,
R.
Ni
, and
M.
Dijkstra
,
J. Chem. Phys.
133
,
244115
(
2010
).
23.
T.
Schilling
,
S.
Dorosz
,
H. J.
Schöpe
, and
G.
Opletal
,
J. Phys.: Condens. Matter
23
,
194120
(
2011
).
24.
W.
Wöhler
and
T.
Schilling
,
Phys. Rev. Lett.
128
,
238001
(
2022
).
25.
P. N.
Pusey
and
W.
van Megen
,
Phys. Rev. Lett.
59
,
2083
(
1987
).
26.
S. M.
Underwood
,
J. R.
Taylor
, and
W.
Van Megen
,
Langmuir
10
,
3550
(
1994
).
27.
T.
Palberg
,
J. Phys.: Condens. Matter
11
,
R323
(
1999
).
28.
C. P.
Royall
,
W. C. K.
Poon
, and
E. R.
Weeks
,
Soft Matter
9
,
17
(
2013
).
29.
T.
Kawasaki
and
H.
Tanaka
,
Proc. Natl. Acad. Sci. U. S. A.
107
,
14036
(
2010
).
30.
L.
Filion
,
R.
Ni
,
D.
Frenkel
, and
M.
Dijkstra
,
J. Chem. Phys.
134
,
134901
(
2011
).
31.
J.
Russo
,
A. C.
Maggs
,
D.
Bonn
, and
H.
Tanaka
,
Soft Matter
9
,
7369
(
2013
).
32.
G.
Fiorucci
,
G. M.
Coli
,
J. T.
Padding
, and
M.
Dijkstra
,
J. Chem. Phys.
152
,
064903
(
2020
).
33.
S.
Auer
,
W.
Poon
, and
D.
Frenkel
,
Phys. Rev. E
67
,
020401
(
2003
).
34.
D.
Frenkel
and
B.
Smit
,
Understanding Molecular Simulation: From Algorithms to Applications
, 2nd ed. (
Academic Press
,
San Diego
,
2002
).
35.
J. M.
Polson
,
E.
Trizac
,
S.
Pronk
, and
D.
Frenkel
,
J. Chem. Phys.
112
,
5339
(
2000
).
36.
P. N.
Pusey
and
W.
Van Megen
,
Nature
320
,
340
(
1986
).
37.
S.
Alexander
,
P. M.
Chaikin
,
P.
Grant
,
G. J.
Morales
,
P.
Pincus
, and
D.
Hone
,
J. Chem. Phys.
80
,
5776
(
1984
).
38.
K.
Kremer
,
M. O.
Robbins
, and
G. S.
Grest
,
Phys. Rev. Lett.
57
,
2694
(
1986
).
39.
M. O.
Robbins
,
K.
Kremer
, and
G. S.
Grest
,
J. Chem. Phys.
88
,
3286
(
1988
).
40.
Y.
Monovoukas
and
A. P.
Gast
,
J. Colloid Interface Sci.
128
,
533
(
1989
).
41.
E. B.
Sirota
,
H. D.
Ou-Yang
,
S. K.
Sinha
,
P. M.
Chaikin
,
J. D.
Axe
, and
Y.
Fujii
,
Phys. Rev. Lett.
62
,
1524
(
1989
).
42.
S.
Hamaguchi
,
R. T.
Farouki
, and
D. H. E.
Dubin
,
Phys. Rev. E
56
,
4671
(
1997
).
43.
A.-P.
Hynninen
and
M.
Dijkstra
,
Phys. Rev. E
68
,
021407
(
2003
).
44.
A.
Yethiraj
and
A.
van Blaaderen
,
Nature
421
,
513
(
2003
).
45.
C. P.
Royall
,
M. E.
Leunissen
, and
A.
van Blaaderen
,
J. Phys.: Condens. Matter
15
,
S3581
(
2003
).
46.
M. F.
Hsu
,
E. R.
Dufresne
, and
D. A.
Weitz
,
Langmuir
21
,
4881
(
2005
).
47.
C. P.
Royall
,
M. E.
Leunissen
,
A.-P.
Hynninen
,
M.
Dijkstra
, and
A.
van Blaaderen
,
J. Chem. Phys.
124
,
244706
(
2006
).
48.
D.
El Masri
,
P.
van Oostrum
,
F.
Smallenburg
,
T.
Vissers
,
A.
Imhof
,
M.
Dijkstra
, and
A.
van Blaaderen
,
Soft Matter
7
,
3462
(
2011
).
49.
F.
Smallenburg
,
N.
Boon
,
M.
Kater
,
M.
Dijkstra
, and
R.
van Roij
,
J. Chem. Phys.
134
,
074505
(
2011
).
50.
T.
Kanai
,
N.
Boon
,
P. J.
Lu
,
E.
Sloutskin
,
A. B.
Schofield
,
F.
Smallenburg
,
R.
van Roij
,
M.
Dijkstra
,
D. A.
Weitz
 et al,
Phys. Rev. E
91
,
030301
(
2015
).
51.
S.
Arai
and
H.
Tanaka
,
Nat. Phys.
13
,
503
(
2017
).
52.
M.
Chaudhuri
,
E.
Allahyarov
,
H.
Löwen
,
S. U.
Egelhaaf
, and
D. A.
Weitz
,
Phys. Rev. Lett.
119
,
128001
(
2017
).
53.
K.
van Gruijthuijsen
,
M.
Obiols-Rabasa
,
M.
Heinen
,
G.
Nägele
, and
A.
Stradner
,
Langmuir
29
,
11199
(
2013
).
54.
T. E.
Kodger
,
R. E.
Guerra
, and
J.
Sprakel
,
Sci. Rep.
5
,
14635
(
2015
).
55.
M.
Leunissen
, Ph.D. thesis,
2007
.
56.
D.
Frenkel
and
A. J. C.
Ladd
,
J. Chem. Phys.
81
,
3188
(
1984
).
57.
P.-R.
ten Wolde
,
M. J.
Ruiz-Montero
, and
D.
Frenkel
,
Faraday Discuss.
104
,
93
(
1996
).
58.
M
de Jager
(
2022
). “
Crystal nucleation of highly-screened charged colloids
,”
Utrecht University
.

Supplementary Material

You do not currently have access to this content.