Molecular Dynamics Simulations Studies of the Surfactant Role in

Growth Mechanism of Gold Nanorods via Seed-Mediated Methods:

Advances and Open Problems
José Adriano da Silva,a Paulo Augusto Netz,b Mario R. Meneghetti,*a
a
Grupo de Catálise e Reatividade Química - GCaR, Instituto de Química e Biotecnologia, Universidade Federal de Alagoas,
Av. Lourival de Melo Mota, s/n, CEP 57072-970, Maceió, Alagoas, Brazil.
b
Institute of Chemistry - Federal University of the Rio Grande do Sul, Av. Bento Gonçalves, 9500, CEP 91501-970, Porto
Alegre, Rio Grande do Sul, Brazil.

KEYWORDS. Molecular dynamics, gold nanorods synthesis, CTAB, anisotropic growth mechanism.

ABSTRACT: Gold nanorods (AuNRs) are an important class of nanoparticles that have unique properties and a wide potential of
applications, and therefore the discovery of colloidal synthesis, which allowed their preparation under satisfactory conditions of
morphology, monodispersity and yield has triggered a wave of studies on the application of their properties, while the mechanism
of formation of AuNRs in colloidal synthesis remains a matter of constant interest. Many experimental techniques have been used
to elucidate the mechanism of anisotropic growth over time, and more recently molecular dynamics (MD) simulations have been
used for help elucidate this problem. By working together to compare the simulation results, experimental data and current
hypotheses, it is possible to verify the success of the simulations in suggesting several new aspects of the anisotropic growth
mechanism of AuNRs. In this Review, we present a historical overview of the evolution of mechanism proposals from the
introduction of the seed-mediated synthesis method to recent developments resulting from MD simulations. We point out the merits
and limitations of the different mechanisms, show our contributions in the area, and point to remain open questions about
understanding the anisotropic growth of AuNRs.

INTRODUCTION
Throughout the history, the methods of obtaining and
manipulating gold nanoparticles (AuNPs) were rudimentary, until
in the twentieth century, advances were made thanks to the
development of efficient synthesis methods that allowed the
controlled manipulation of these structures opening wide
possibilities of applications.1 In particular, the seed-mediated
synthesis method introduced by Murphy et al. in 2001, 2 and later
refined by Nikoobakht and El-Sayed in 2003,3 stood out as one of
the most effective for obtaining good yield and efficient control
over morphology and is therefore the most widely used today.
Generically, in the seed-mediated synthesis of AuNRs, the
growth of these anisotropic nanoparticles is mediated by the
addition of metallic gold atoms at the surface of previously
prepared small gold nanoparticles (seeds), by a controlled
reduction of Au(I) species at the surface of the seeds that grow in
an anisotropic way due to the presence of
cetyltrimethylammonium bromide (CTAB) as a growth-driving
agent. Indeed, many studies of these standard synthesis methods
and adaptations thereof have appeared in the literature. In
particular, the effects of the seed size, 4 cosurfactants,5 additives,6
temperature,7 surfactant chain length,8 and headgroup structure9
have been investigated.
Details of the two procedures that generate both types of AuNRs
are highlighted in Table 1. Despite the rich literature of studies
applied with AuNRs, there is still a vigorous field of research on
the mechanism of formation of these nanoparticles in colloidal
synthesis, and particularly the role of surfactant and silver in
anisotropic growth is a constant research and debate subject.

Table 1. General details for preparing AuNRs via seed-mediated synthesis.

Synthesis method Seed solution Seed shape Growth solution Crystallinity of Aspect ratiob Selectivitya
the AuNRs
(AR)

Murphy and NaBH4, Decahedral Ascorbic acid, Penta-twinned 6 to 20 ca. 15%

coworkers2 HAuCl4 and HAuCl4 and with pentagonal
citrate CTAB cross-section
El-Sayed and NaBH4, Cuboctahedral Ascorbic acid, Single-crystal 1.5 to 5.0 ca. 90%
coworkers3 HAuCl4 and HAuCl4, CTAB with octagonal
CTAB and AgNO3 cross-section
 a
Relative to the number of nanoparticles formed. bAspect ratio (AR) is proportion between the length/width.
THE HISTORY OF GROWTH MECHANISMS OF GOLD
NANORODS IN COLLOIDAL SYNTHESIS
The study of the role of the CTAB surfactant in the AuNRs
anisotropic growth mechanism has evolved with a variety of
formulated and reformulated (or discarded) hypotheses with
advances in more detailed knowledge of AuNRs synthesis and
gold/surfactant/water interface properties.
One of the first mechanisms proposes that CTAB micelles, in
the growth solution, would have the shape of cylindrical micelles
and act as a soft template (Figure 1a), 10 but it was later
demonstrated that AuNRs could be obtained even at
concentrations below the CTAB critical micelar concentration
(CMC),11 and it has also been shown that seed size at symmetry
break (4-6 nm) is larger than CTAB micelle diameters and
therefore could not function as a soft template. 12
Outher groups propose that the CTA + headgroup binds to the
side surface with some preference due a sterics effect, because the
Au atom spacing on the side faces (100) is more comparable to
the size of the CTA+ headgroup than the close-packed (111) face
from AuNRs tips. Such binding stabilizes the side faces, which
have relatively large surface energy compared to tips facets and
allows preferential material addition in the tips. 13,14
The other hypothesis is from Mulvaney and co-workers, 15 that
suppose that a AuNRs tips electric-field directed the anisotropic
deposition. In this mechanism, [AuCl 4] is bound to CTAB
micelles and hence reduced to [AuCl 2]-CTAB micelles. This
complex binds to the CTAB-capped seed particles through
collisions which are controlled by the electric double layer
between the positively charged seed and negatively charged
[AuCl2] on the CTAB micelles. The collisions are faster at the
tips than the sides of the seeds and thus facilitate the rod-shape
growth.
Murphy and co-workers proposed in 2003, 8 a mechanism
whereby CTAB surfactants could preferentially adsorb on the side
facets of the growing AuNR. They stated that when AuNRs begin
to develop anisotropy, bilayer formation occurs on the side facets,
Figure 1. Ilustration of (a) soft template and (b) zipping growth mechanism. Reproduced from ref 26. Copyright 2018 American Chemical
Society.
THE APPLICATION OF MOLECULAR DYNAMICS ON
GOLD NANORODS SYNTHESIS MECHANISMS
Meena and Sulpizi,21-23 pioneered the study of MD focused on
the anisotropic growth mechanism of AuNRs in colloidal
synthesis. They created one representing the conditions of the
gold/surfactant/water interface (Figure 2a), and thus to verify
differences in adsorption that justify anisotropic growth.
According to the results, the arrangement allows the formation
of anchored cylindrical micelles on the surface of the AuNRs,
generating water-ion channels between adjacent micelles
making it difficult for the gold source Au(I) to access these facets,
while favoring growth on the facets of the AuNRs tips, where
there is some undefined CTAB structure, that would allow greater
access from the gold source. The reasons for CTAB's increased
adherence to side facets are generally attributed to experimental
evidence that bromides selectively adsorb on different gold
surface crystallographic facets, and stronger on facets (100), such
as those present on AuNR sides16 and thus the preferential binding
of CTAB to the side facets would be mediated by the adsorption
of bromides on these facets. This proposed mechanism became
known as the zipping mechanism (Figure 1b), and has been
adopted as the main reference for the mechanism in literature.
Other studies contribute to the elucidation of the growth
mechanism by revealing important aspects of colloidal synthesis
and showing details of the CTAB/Au surface interaction.
Edgar and coworkers showed, using UV-visible absorption that
the Au source HAuCl4 reacts with the bromide of CTAB and form
the species [AuBr4] which is reduced to [AuBr 2], that is a Au(I)
precursor species in the synthesis.17
Hafner and co-workers used surface-enhanced Raman
spectroscopy to confirm the existence of Au-Br- interactions and
verified that the adsorbed CTAB forms bilayer and with a
perturbation of bilayer stability, can form a “collapsed bilayer” by
detecting the interactions between the alkane chains of the CTA +
moiety and the AuNR surface.18
Vivek and Burgess performed electrochemical experiments on
the adsorption of a quaternary ammonium bromide surfactant onto
the (100) and (111) flat gold surfaces and demonstrated that there
is no significant difference in the adsorption behavior of the
surfactants onto the two crystal planes, despite different levels of
bromide adsorption, and the authors concluded that there is no
thermodynamic basis for invoking a model of preferential
adsorption of a surfactant onto the different low-index gold facets
in the presence of bromide ions.19,20
(Figure 2b) and not a typical bilayer, as commonly reported in
the literature. The authors argue that these channels are a
possible space for the diffusion of Au(I) species towards the
gold surface. Furthermore, they showed that these channels are
relatively different in thickness depending on the facet in which
the micelles are anchored, with the largest channels being
observed on Au(111) surfaces. The authors emphasize that the
channel width is inversely proportional to the amount of
bromides adsorbed on the facets.
 The zipping mechanism is in agreement with experimental
data showing the presence of a CTAB bilayer on the surface of
mature AuNRs,18 but admitting that this compact bilayer exists
throughout the process is in contrast to the lateral growth of
AuNRs observed experimentally in the early stages of
anisotropic growth,24 as it would imply that [AuBr 2] species
leave the aqueous medium and spontaneously cross a
hydrophobic barrier, a process which must be very unfavorable.
The Meena and Sulpizi mechanism is a very coherent way of
conceiving the presence of lateral and extremity growth of
growing AuNRs. However, all simulation models adopted by
Meena and Sulpizi are flat surfaces, disregarding the effect of
the curvature present on the AuNRs tips and therefore may be
incomplete, as the differences in intermicellar channel thickness
on any type of flat surface they are small to justify the
pronounced anisotropic growth in the tips. 24 Moreover, another
important point in Meena and Sulpizi's results is the fact that
they do not observe a CTAB bilayer, an observation widely
reported in the literature on mature AuNRs.

Figure 2. (a) Meena and Sulpizi simulation model. (b) CTAB adsortion on gold surface with different crystalographic indexes. Reproduced
from ref 22 and 24. Copyright 2017 American Chemical Society.

In other studies, we have shown that the condition that
differentiates the formation of adjacent cylindrical micelles from
the formation of a CTAB bilayer is the largest amount of
bromine ions at the Au/CTA+ interface in this latter structure
(Figure 3a).25,26 Subsequently, we studied the effect of curvature
on the structure of the adsorbed layer under the same conditions
as on the flat surface27 and found that the CTAB layer has a
lower density on the curved surface because part of the CTA + is
not in the adsorbed layer (Figure 3b) and in planar surface all
CTAB remain adsorbed (Figure 3c). This theoretical prediction
that CTAB density should be lower at the tips of AuNRs was
confirmed by Huang and co-workers 28 using the Electron
Energy Loss Spectroscopy technique in an Aberration-corrected
Scanning Transmission Electron Microscopy.
To compare the size of the channels on the flat and curved
surfaces, we delimited a cubic region positioned in the channel
and compared the size of the channels by measuring the number
of water molecules inside the box. We found that the
crystallographic index does not significantly affect the size of
the channels nor the structure of the adsorbed layer on the flat
surfaces, but the curvature makes the channels larger (Figure 4).

Figure 3. Snapshots of the top view (z-axis) of the MD simulations on a (a) curved surface and (b) flat surface (100). The water molecules
and the bromide ions are omitted for clarity. (c) Number of water molecules inside the red box during the simulation. Reproduced from ref
27 and 28. Copyright 2017 American Chemical Society.
Figure 4. A Channel structure on flat and curved surfaces. B Bilayer structure on planar surface. C Frontal view of the channels on planar
and curved surfaces. D Channel size measurement by the amount of water molecules inside the box. Reproduced from ref 27. Copyright
2017 American Chemical Society.

Finally, we use umbrella sampling simulations and measure
the energy barrier of the species passage [AuBr 2] through the
channels on the flat and curved surfaces and the membrane
region (Figure 4A, 4B, 4C and 4D). We show that the energy
barrier for the Au(I) passage is smaller on the curved surface
than in the planar surface and that this should be a major factor
for the anisotropic deposition present in the formation of
AuNRs.
With this we propose a growth mechanism, which in AuNRs
single crystal, after the symmetry break caused by the presence
of silver, is formed cylindrical micelles with channels on the
surfaces of the sides and tips of the AuNR and therefore larger
channels and lower energy barrier for Au(I) deposition at the
tips due to curvature. As in mature AuNR a CTAB bilayer is
experimentally detected, then there must be a process of
channel-to-bilayer transition during growth. As the condition
that differentiates the existence of channel micelles from the
bilayer is the largest number of bromide at the Au/CTA +
interface, then the transition must be associated with the
bromine accumulation at the interface and this is plausible
because the process of reducing [AuBr2] to Au(0) releases
bromide ions in loco (Figure 5).
Figure 5. (A) Energy profile (potential of mean force, PMF) of umbrella sampling on different surfaces with a 5-site model. Passage of
[AuBr2] through the channels on (B) flat and (C) curved surfaces. (D) Diffusion of [AuBr 2] through the hydrophobic layer on a flat
surface. The water molecules and the bromide ions are omitted for clarity. Illustration of the growth stages of a single-crystal AuNR during
seed-mediated colloidal synthesis. Reproduced from ref 26 and 27. Copyright 2019 American Chemical Society.
THE ROLE OF SILVER IN GOLD NANORODS GROWTH
MECHANISM
The presence of silver in the form of silver nitrate traces, in the
growth solution, has generated several hypotheses to explain its
effect on the formation of simple crystalline AuNRs. Much of the
motivation comes from the Nikoobakht and El-Sayed procedure 3
which showed that variation in silver concentration in the growth
solution affects the AuNR AR formed, more specifically AuNRs
are not formed in the absence of silver and the increase the
presence of silver to a certain extent increases the AR.
Liu and Guyot-Sionnest29 observed that Ag(I) ions in CTAB
aqueous solution can only be reduced to Ag(0) by ascorbic acid at
a pH above pH = 8.7 whereas under typical conditions of AuNR
synthesis, the pH of the growth solution is around 3. Thus, the
Ag(I) ions are not reduced to Ag(0), but could be deposited on the
gold surface under potential deposition (UPD). Considering the
arrangement of the gold atoms in the different low index facets,
the deposition of Ag(I) should be more favored in the facets (110)
and (100) present on the sides of the AuNRs, due to the
coordination number of the Ag atoms is 4, while the co-ordination
number for deposition in (111) tips facet is 3. According to the
authors, silver deposition on a surface has the effect of inhibiting
the Au(I) reduction rate on the AuNP surface and thus,
particularly in AuNRs, Ag(I) deposition on the sides could be the
promoter of anisotropic growth.
+
Hubert and co-workers argued that the CTA-Br-Ag complex is
present in situ under the conditions of the growth solution and
they showed that the combination of CTA-Br-Ag + (ex situ
generated) with CTAB can be used in the synthesis of AuNRs,
without the addition of AgNO3.30 On the other hand, Cao and co-
workers found that the conditions for the formation of the CTA-
Br-Ag+ complex in solution, the ratio of CTAB/AgNO3 must be
above 1.5:1 (10000 x greater than found in the conditions of the
growth solution)31 and therefore it is questionable whether the
complex actually exists under the conditions of the growth
solution.
One of the key points in the discussion of AuNRs synthesis
mechanism is the breaking symmetry of seed towards an
anisotropic form. Walsh and co-workers 12 showed that in the
synthesis of single crystalline AuNRs, the symmetry breaking is
the result of the interaction of silver with the seed facets when
they are between 4-6 nm in diameter. And this symmetry breaking
process only occurs when these seeds have simple crystal
structure, on the other hand, seeds containing twinned planes
evolve into AuNS and other byproducts. Tong and co-workers 32
have shown that adding more or less AgNO 3 is the factor that
determines whether the seed breaks symmetry to a larger or
smaller size, and this symmetry breaking size defines AR of
AuNR formed. They also showed that the addition of
supplemental amounts of silver in steps subsequent to symmetry
breaking did not have a significant effect on the AR of formed
AuNRs. Similar conclusion comes from Burrows and co-workers
paper through a fractional factorial design of experiments. 7
Moreau and co-workers33 investigate the role of Ag trace in
AuNRs synthesis and demonstrate that Ag deposits as Ag(0)
preferentially onto higher surface energy ((110) and (100)) that
(111) early in the reaction, a pattern which supports the UPD
hypothesis. The other study how the Ag distribution in the AuNRs
evolves over time and the authors showed that the Ag/Au
coverage rate during the growth decreases, but the AuNR growth
rate at the sides is constant and at the tips decreases over time.
These results indicate that UPD does not affect the restriction of
lateral growth. We can also postulate that the decrease in tip
growth rate may be related to the decrease in tip curvature which
is a consequence of the increase in AuNR diameter.
THE COUTERION EFFECT
The seed-mediated synthesis protocol allows for variant
situations, which also require a mechanistic explanation. Of
particular interest is the effect of the counterion, which shows that
the use of CTAC in place of CTAB, under the same conditions,
generates gold nanospheres rather than AuNRs. 34 This problem
has already been experimentally addressed and it has been
proposed that the ability of bromide to selectively adsorb on
facets generates anisotropy.35 Since this hypothesis is in conflict
with the results of Vivek and Burgess previously mentioned, 19,20
DM simulations by Meena and Sulpizi showed that the different
counterions affect the size of the adsorbed layer, more
specifically, CTAB retains the retained layer, but CTAC cannot
retain the adsorbed layer and therefore does not generate
preferential deposition (Figure 6). 22 On the other hand, we can
verify from literature date comparing the size of the layers that the
CTAB layer is only slightly larger than the CTAC layer, 36,37 and
this is more compatible with the difference of the counterion
dissociation degree of (dissociation degree about 0.24 for Br- and
0.39 for Cl-.38
Figure 6. Meena and co-workers results of couterions effect.
Reproduced from ref 22. Copyright 2016 Royal Chemical
Society.
OPEN PROBLEMS
There are many open questions and not all can be approached
by simulation, but it is possible that the simulation may contribute
to propose solutions. In particular, we can increase the quality of
the model by adding polarization effects, 39 study the presence of
interacting ascorbic acid at the interface and study the equilibrium
between the adsorbed layer and the micelles in solution. Also
interesting are the following questions:
i) The effect of the addition of the
benzyldimethylhexadecylammonium chloride (BDAC) co-
surfactant in the growth solution, in the single crystalline AuNR
synthesis method, which presents very remarkable effects
compared to the standard synthesis with CTAB, as the higher AR,
due to the lower rate of deposition on lateral facets of AuNR, the
lower overall rate of gold reduction during the growth process and
the presence of AuNC as dominant byproducts in contrast to
nanosphere of standard conditions.5
ii) Explain how CTAC can generate AuNR when the reductor
agent is change from ascorbic acid for tartic acid, 40 implied that
the presence of ascorbic acid together with Chloride ions affect
the AuNR formation. This fact have no interpretation following
the previous halide effect propose in literature.
iii) Explain why is necessary a precise ascorbic acid
concentration is within a specific range to allow the generation of
well-formed AuNRs, and allow only 15 % of gold reduction, in
standard conditions, but when ascorbic acid is slowly added in
reaction medium, all gold is reducted.41
iv) Wiley et al. utilizing single-crystal electrodes to determine
what additive(s) in pentatwinned gold nanorod syntheses are
responsible for facet-selective atomic addition observed a major
deposition for Au(111) relative to Au(100), but the growth rate
observe in AuNR aspect ration is several times greater, what
showth that outher factors that only facet seletivety is related to
AuNR penta-twinned anisotropic growth.42
CONCLUSIONS
We show the diversity of approaches to address the growth
mechanism of AuNR growth in colloidal synthesis and show how
MD simulations contribute to revealing new aspects of the growth
mechanism.
We point to many data without a definitive explanation that can
be elucidated with the help of MD simulations, generating new
experimental predictions while contributing to more efficient
AuNR surface functionalization approaches.
ASSOCIATED CONTENT
Supporting Information. The Supporting Information is
available free of charge on the ACS Publications website at
DOI: xxxxxxxxxx.
AUTHOR INFORMATION
Corresponding Author
*E-mail: mrm@qui.ufal.br
ORCID
José Adriano da Silva: 0000-0003-3988-7924
Paulo Augusto Netz: 0000-0003-4242-0591
Mario R. Meneghetti: 0000-0002-0722-8599
Author Contributions
The manuscript was written through the contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
The authors are grateful to the Brazilian Funding agencies
(CNPq, Capes, Fapeal, INCT-Catalise and Capes-BioMol) for
financial support. MRM and PAN thank CNPq for the research
fellowships.
REFERENCES
(1) Lohse, S. E.; Murphy, C. J. The Quest for Shape Control:
A History of Gold Nanorod Synthesis. Chem. Mater. 2013, 25,
1250-1261.
(2) Jana, N. R.; Gearheart, L.; Murphy, C. J. Seed-Mediated
Growth Approach for Shape-Controlled Synthesis of Spheroidal
and Rod-like Gold Nanoparticles Using a Surfactant Template.
J. Adv. Mater. 2001, 13, 1389-1393.
(3) Nikoobakht, B.; El-Sayed, M. A. Preparation and Growth
Mechanism of Gold Nanorods (NRs) Using Seed-Mediated
Growth Method. Chem. Mater.2003, 15, 1957-1962.
(4) Yoon, S.; Lee, B.; Yun, J.; Han, J. G.; Lee, J.; Lee, J. H.
Systematic study of interdependent relationship on gold nanorod
synthesis assisted by electron microscopy image analysis.
Nanoscale 2017, 9, 7114.
(5) Hatakeyama, Y.; Sasaki, K.; Judai, K.; Nishikawa, K.;
Hino, K. Growth Behavior of Gold Nanorods Synthesized by
the Seed-Mediated Method: Tracking of Reaction Progress by
Time-Resolved X-ray Absorption Near-Edge Structure, Small-
Angle X-ray Scattering, and Ultraviolet-Visible Spectroscopy.
J. Phys. Chem. C 2018, 122(14), 7982-7991.
(6) Ye, X.; Jin, L.; Caglayan, H.; Chen, J.; Xing, G.; Zheng,
C.; Doan-Nguyen, V.; Kang, Y.; Engheta, N.; Kagan, C. R.;
Murray, C. B. Improved Size-Tunable Synthesis of
Monodisperse Gold Nanorods through the Use of Aromatic
Additives. ACS Nano 2012, 6, 2804-2817.
(7) Burrows, N. D.; Harvey, S.; Idesis, F. A.; Murphy, C. J.
Understanding the Seed-Mediated Growth of Gold Nanorods
through a Fractional Factorial Design of Experiments.
Langmuir 2017, 33, 1891-1907.
(8) Gao, J.; Bender, C. M.; Murphy, C. J. Dependence of the
Gold Nanorod Aspect Ratio on the Nature of the Directing
Surfactant in Aqueous Solution. Langmuir 2003, 19, 9065-9070.
(9) da Silva, M. G. A.; Meneghetti, M. R.; Denicourt-
Nowicki, A.; Roucoux, A. Tunable hydroxylated surfactants: an
efficient toolbox towards anisotropic gold nanoparticles. RSC
Adv. 2014, 4, 25875- 25879.
(10) Jana, N. R. Gram-Scale Synthesis of Soluble, Near Mo
odisperse Gold Nanorods and Other Anisotropic Nanoparticles.
Small 2005, 1, 875-882.
(11) Garg, N.; Scholl, C.; Mohanty, A.; Jin, R. The Role of
Bromide Ions in Seeding Growth of Au Nanorods. Langmuir
2010, 26 (12), 10271-10276.
(12) Walsh, M. J.; J. Barrow, S. J.; Tong, W.; Funston, A. M.;
Etheridge, J. Symmetry Breaking and Silver in Gold Nanorod
Growth. ACS Nano 2015, 9, 715-724.
(13) Murphy, C. J.; Sau, T. K.; Gole, A. M.; Orendorff, C. J.;
Gao, J.; Gou, L.; Hunyadi, S. E.; Li, T. Anisotropic Metal
Nanoparticles: Synthesis, Assembly, and Optical Applications.
J. Phys. Chem. B 2005, 109, 13857-13870.
(14) Pan, B.; Cui, D.; Ozkan, C.; Xu, P.; Huang, T.; Li, Q.;
Chen, H.; Liu, F.; Gao, F.; He, R. DNA-Templated Ordered
Array of Gold Nanorods in One and Two Dimensions. J. Phys.
Chem. 2007, 111, 12572.
(15) Perez-Juste, J.; Liz-Marzan, L. M.; Carnie, S.; Chan, D.
Y. C. ; Mulvaney, P. Electric‐Field‐Directed Growth of Gold
Nanorods in Aqueous Surfactant Solutions. Adv. Funct. Mater.
2004, 14, 571.
(16) Magnussen, O. M. Ordered Anion Adlayers on Metal
Electrode Surfaces. Chem. Rev. 2002, 102, 679-726.
(17) Edgar, J. A.; McDonagh, A. M.; Cortie, M. B. Formation
of Gold Nanorods by a Stochastic “Popcorn” Mechanism. ACS
Nano 2012, 6(2), 1116-1125.
(18) Lee, S.; Anderson, L. J. E.; Payne, C. M.; Hafner, J. H.
Structural Transition in the Surfactant Layer that Surrounds
Gold Nanorods as Observed by Analytical Surface-Enhanced
Raman Spectroscopy. Langmuir 2011, 27, 14748-14756.
(19) Vivek, J. P.; Burgess, I. J. Quaternary Ammonium
Bromide Surfactant Adsorption on Low-Index Surfaces of Gold.
1. Au(111). Langmuir 2012, 28(11), 5031-5039.
(20) Vivek, J. P.; Burgess, I. J. Quaternary Ammonium
Bromide Surfactant Adsorption on Low-Index Surfaces of Gold.
2. Au(100) and the Role of Crystallographic-Dependent
Adsorption in the Formation of Anisotropic Nanoparticles.
Langmuir 2012, 28(11), 5040-5047.
(21) Meena, S. K.; Sulpizi, M. Understanding the
Microscopic Origin of Gold Nanoparticle Anisotropic Growth
from Molecular Dynamics Simulations. Langmuir 2013, 29,
14954-14961.
(22) Meena, S. K.; Sulpizi, M. From Gold Nanoseeds to
Nanorods: The Microscopic Origin of the Anisotropic Growth.
Angew. Chem., Int. Ed. 2016, 55, 11960-11964.
(23) Meena, S. K.; Celiksoy, S.; Schafer, P.; Henkel, A.; So
nnichsen, C.; Sulpizi, M. The role of halide ions in the
anisotropic growth of gold nanoparticles: a microscopic,
atomistic perspective. Phys. Chem. Chem. Phys. 2016, 18,
13246-13254.
(24) Park, K.; Drummy, L. F.; Wadams, R. C.; Koerner, H.;
Nepal, D.; Fabris, L.; Vaia, R. A. Growth Mechanism of Gold
Nanorods. Chem. Mater. 2013, 25, 555-563.
(25) da Silva, J. A.; Dias, R. P.; da Hora, G. C. A.; Soares, T.
A.; Meneghetti, M. R. Molecular dynamics simulations of
cetyltrimethylammonium bromide (CTAB) micelles and their
interactions with a gold surface in aqueous solution. J. Braz.
Chem. Soc. 2018, 29, 191-199.
(26) da Silva, J. A.; Meneghetti, M. R.New Aspects of the
Gold Nanorod Formation Mechanism via Seed-Mediated
Methods Revealed by Molecular Dynamics Simulations.
Langmuir 2018, 34, 366-375.
(27) da Silva, J. A.; Netz, P. A.; Meneghetti, M. R. Growth
mechanism of gold nanorods: the effect of tip-surface curvature
as revealed by molecular dynamics simulations. Langmuir
Langmuir 2020, 36, 1, 257-263.
(28) Janicek, B. E.; Hinman, J. G.; Hinman, J. J. H.; Bae, S. ;
Wu, M.; Turner, J.; Chang, H.; Park, E.; Lawless, R.; Suslick, K.
S.; Murphy, C. J.; Huang, P. Y. Quantitative Imaging of Organic
Ligand Density on Anisotropic Inorganic Nanocrystals.
NanoLetters 2019, 19, 9, 6308-6314.
(29) Liu, M.; Guyot-Sionnest, P. Mechanism of Silver(I)-
Assisted Growth of Gold Nanorods and Bipyramids. J. Phys.
Chem. B 2005, 109, 22192-22200.
(30) Hubert, F.; Testard, F.; Spalla, O.
Cetyltrimethylammonium Bromide Silver Bromide Complex as
the Capping Agent of Gold Nanorods. Langmuir 2008, 24,
9219-9222.
(31) Liu, X. H.; Luo, X. H.; Lu, S. X.; Zhang, J. C.; Cao, W.
L. A novel cetyltrimethyl ammonium silver bromide complex
and silver bromide nanoparticles obtained by the surfactant
counterion. J. Colloid Interface Sci. 2007, 307, 94-100.
(32) Tong, W.; Walsh, M. J.; Mulvaney, P.; Etheridge, J.;
Funston, A. M. Control of Symmetry Breaking Size and Aspect
Ratio in Gold Nanorods: Underlying Role of Silver Nitrate. J.
Phys. Chem. C 2017, 121, 3549-3559.
(33) Moreau, L. M.; Jones, M. R.; Roth, E. W.; Wu, J.;
Kewalramani, S.; O’Brien, M. N.; Chen, B.-R.; Mirkin, C. A.;
Bedzyk, M. J. The role of trace Ag in the synthesis of Au
nanorods. Nanoscale 2019, 11, 11744.
(34) Sau, T. K.; Murphy, C. Role of ions in the colloidal
synthesis of gold nanowires. J. Philos. Mag. 2007, 87, 2143-
2158.
(35) Du Chene, J. S.; Niu, W.; Abendroth, J. M.; Sun, Q.;
Zhao, W.; Huo, F.; Wei, D. Halide Anions as Shape-Directing
Agents for Obtaining High-Quality Anisotropic Gold
Nanostructures. Chem. Mater. 2013, 25 (8), 1392-1399.
(36) Kawasaki, H.; Nishimura, K.; Arakawa, R. Influence of
the Counterions of Cetyltrimetylammonium Salts on the
Surfactant Adsorption onto Gold Surfaces and the Formation of
Gold Nanoparticles. J. Phys. Chem. C 2007, 111, 2683-2690.
(37) Hore, M. J. A.; Ye, X.; Ford, J.; Gao, Y.; Fei, J.; Wu, Q.;
Rowan, S. J.; Composto, R. J.; Murray, C. B.; Hammouda, B.
Probing the Structure, Composition, and Spatial Distribution of
Ligands on Gold Nanorods. Nano Lett. 2015, 15 (9), 5730-5738.
(38) Lutz-Bueno, V.; Pasquino, R.; Liebi, M.; Kohlbrecher, J.;
Fischer, P. Viscoelasticity Enhancement of Surfactant Solutions
Depends on Molecular Conformation: Influence of Surfactant
Headgroup Structure and Its Counterion. Langmuir 2016, 32
(17), 4239-4250.
(39) Geada, I. L.; Ramezani-Dakhel, H.; Jamil, T.; Sulpizi,
M.; Heinz, H.. Insight into induced charges at metal surfaces
and biointerfaces using a polarizable Lennard-Jones potential.
Nat Commun 2018, 9, 716.
(40) Roy, D.; Xu, Y.; Rajendra, R.; Wu, L.; Bai, P.; Nirmalya
Ballav, N. Gold Nanoearbuds: Seed-Mediated Synthesis and the
Emergence of Three Plasmonic Peaks. J. Phys. Chem. Lett.
2020, 11, 9, 3211–3217.
(41) Kozek, K. A.; Kozek, K. M.; Wu, W.-C.; Mishra, S. R.;
Tracy, J. B. Large-Scale Synthesis of Gold Nanorods through
Continuous Secondary Growth. Chem. Mater. 2013, 25, 22,
4537-4544.
 (42) Brown, M.; J. Wiley, B. J. Bromide Causes Facet-
Selective Atomic Addition in Gold Nanorod Syntheses. Chem.
Mater. 2020, 32, 15, 6410-6415.

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