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Article
Nucleation and Growth Kinetics from LaMer Burst Data
Daniel B. K. Chu, Jonathan S Owen, and Baron Peters
J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.7b08368 • Publication Date (Web): 20 Sep 2017
Downloaded from http://pubs.acs.org on September 24, 2017

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Page 1 of 14 The Journal of Physical Chemistry

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7 Nucleation and Growth Kinetics from LaMer Burst Data
8
9 Daniel B. K. Chu,1 Jonathan S. Owen,2 Baron Peters1,3*
10 1Department of Chemical Engineering, University of California, Santa Barbara, CA 93106
11
2Department of Chemistry, Columbia University, New York, NY 10027
12
13 3Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA 93106
14
15
16 ABSTRACT: In LaMer burst nucleation, the individual nucleation events happen en masse, quasi-simultaneously, and at
17 nearly identical homogeneous conditions. These properties make LaMer burst nucleation important for applications that
18 require monodispersed particles and also for theoretical analyses. Sugimoto and coworkers predicted that the number of
19 nuclei generated during a LaMer burst depends only on the solute supply rate and the growth rate, independent of the nu-
20 cleation kinetics. Some experiments confirm that solute supply kinetics control the number of nuclei, but flaws in the origi-
21 nal theoretical analysis raise questions about the predicted roles of growth and nucleation kinetics. We provide a rigorous
22 analysis of the coupled equations that govern concentrations of nuclei and solutes. Our analysis confirms that the number
23 of nuclei is largely determined by the solute supply and growth rates, but our predicted relationship differs from that of
24 Sugimoto et al. Moreover, we find that additional nucleus-size-dependent corrections should emerge in systems with slow
25 growth kinetics. Finally, we show how the nucleation kinetics determine the particle size distribution. We suggest that
26 measured particle size distributions might therefore provide ways to test theoretical models of homogeneous nucleation
kinetics.
27
28
29
30 INTRODUCTION complications can be mitigated, one could exploit the natu-
31 rally controlled conditions during a LaMer burst to develop
In most nucleation processes, the kinetics are extremely
32 difficult to model because nucleation occurs heterogene- accurate models for the nucleation and growth kinetics.
33 ously at sites with unknown characteristics.1-2 In contrast, Recent advances have added new ways to generate, ana-
34 the in situ source of supersaturation in a LaMer burst nu- lyze, and model the data from these complex processes. In
35 cleation process yields a massive population of nuclei all particular, we mention three experimental techniques:
36 born simultaneously, under identical conditions, and most (i) New time-resolved pair-distribution techniques can
37 likely by homogeneous nucleation. As first understood by track the PSD even during the short nucleation burst
38 LaMer and Dinegar,3-4 a steady supply of solutes initially stages.14-17
39 drives supersaturation toward the metastable zone limit. (ii) New syntheses use precursors that decompose with
40 Near the edge of the metastable zone, the nucleation rate tunable kinetics15, 17-19 to control the in situ homoge-
41 skyrockets and a large population of nuclei are almost neous solute supply rate.
42 simultaneously born. As these nuclei begin to grow, they (iii) For semiconductor quantum dots, electron transfer
43 drive the supersaturation downward again and thereby and Forster resonance energy transfer properties can
arrest all further nucleation. The distinct stages of a LaMer be used to characterize the thickness, density, and
44
burst are shown above in the table of contents figure. In composition of the organic ligands.20
45
the figure, C(t) is the solute concentration, and Cm is the These experiments provide opportunities to synthesize
46
maximum in C(t), attained at the time tm. monodisperse nanoparticles with tunable properties un-
47 der precisely controlled conditions and to probe the PSD
48 Many experiments4-7 qualitatively confirm the behavior
in the table of contents figure, and the separate nucleation before aggregation and ripening processes can occur.
49 Unlike processes that are dominated by heterogeneous
and growth stages of a LaMer burst are a widely recog-
50 and/or secondary nucleation, the kinetics of LaMer burst
nized route to monodisperse particles.8-11 However, quan-
51 nucleation can be precisely and reliably controlled through
titative predictions of the number, size, and polydispersity
52 the rate of the solute generation reaction, e.g. by adjusting
in the particle size distribution (PSD) face many complica-
53 tions. In some experiments, the injection of solutes or re- the solvent pH, ionic strength, temperature, solute precur-
54 ducing agents creates a supersaturated plume where nu- sor ligands, etc.8 The well-defined nature of the conditions
55 clei can form before nucleation begins in the bulk solu- during homogeneous nucleation and the wealth of kinetic
56 tion.5, 10 Even under the most carefully controlled condi- trends that can be examined make LaMer burst nucleation
57 tions, aggregation and ripening processes begin to modify ideal for theoretical studies. Thus far, LaMer burst studies
58 the PSD shortly after the nucleation burst.12-13 If these have focused on inorganic nanoparticle syntheses, but sim-
59 ilar ideas will surely impact future efforts to create mono-
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disperse nanocrystalline pharmaceuticals,21 food prod- predicts that the total number of nuclei does not depend
1 ucts,22 and perhaps building blocks for growing larger on any aspect of the nucleation kinetics, and (ii) it predicts
2
3
crystals by oriented attachment.23 a linearly increasing relationship between the Q and pT∞ .
Current models of LaMer burst nucleation span several
4 levels of detail: stochastic population balance models,24-25 These key predictions have been corroborated by several
5 deterministic species balance models,7, 26-27 and models experiments on AgCl and AgBr nucleation.8, 28-29 Experi-
6 that include additional ripening and aggregation process- ments on chalcogenides also show an increasing relation-
7 es.25 Sugimoto introduced an extremely simple model of ship between G and pT∞ , but there are significant depar-
8 LaMer burst nucleation that is readily used for interpreting
tures from the linear relationship in equation (5).15, 17, 19
9 experiments.8, 28 This paper examines the assumptions and
Sugimoto and others have used equation (5) to infer the
10 analysis behind the Sugimoto model to motivate certain
growth rates, but as shown below certain problems in the
11 improvements to its accuracy, versatility, and predictive
derivation of equation (5) suggest that the observed slope
12 power.
is not actually 1/G.
13
14 THE MODEL OF SUGIMOTO
EXTENSION OF THE SUGIMOTO MODEL
15 Sugimoto’s starting point is a pair of differential equa-
Several aspects of the model by Sugimoto et al. can po-
16 tions that govern the concentration of solutes C(t) and the
tentially be improved. An obvious point of concern is the
17 population of nuclei pT(t):
assumption of a size and concentration independent
18 growth rate G. The concentration dependence of G may be
19 dC
= Q − J n * −GpT (1) negligible because the concentration changes are small
20 dt during the nucleation stage, but the size dependence of G is
21 probably important. When nuclei are still near their critical
22 and size n* they grow by random attachment and detachment
23 events with very little bias toward attachment.2, 30 As the
24 dpT / dt = J (2) nuclei become much larger than their critical size the driv-
25 ing force for growth approaches its macroscopic limit, but
26 Here n* is the critical nucleus size, J is the nucleation rate, growth rates may still depend on size through diffusion
27 pT is the number of post-critical nuclei per volume, G is the controlled attachment kinetics (where the boundary layer
28 growth rate in solutes attached per time per nucleus, and Q thickness is proportional to the particle radius) or through
29 is the solute supply rate per volume. Equation (1) is a spe- surface reaction limited attachment (where the rate of
30 cies balance equation for the solutes and equation (2) is attachment is proportional to the particle surface area).2
31 the definition of the nucleation rate.8, 28 More accurate models with size dependent growth rates
32 To simplify the analysis of events happening during the can be formulated, but they are not as easily solved and
33 nucleation period, Sugimoto assumes (i) that G is a con- used to analyze experimental data. Therefore, we also as-
34 stant, and (ii) that dC/dt vanishes. Using these assump- sume a concentration and size independent attachment
tions, Sugimoto combines equations (1) and (2) yielding frequency G throughout this article.
35
his nucleation balance equation28 This article reexamines Sugimoto’s analyses leading to
36
equations (3) – (5), i.e. to the prediction that the nucleation
37 rate dpT/dt is entirely determined by Q, G, and n*, and that
38 Q = n * dpT / dt + GpT (3)
39 pT∞ is entirely determined by Q and G. Equations (3) - (5)
40 In Sugimoto’s analysis, Q and n* are also treated as con- warrant reexamination for two reasons:
41 stants. Sugimoto then solves equation (3) as an ODE for t > (i) The counterintuitive irrelevance of the nucleation
42 tm, where tm is the time of maximum solute concentration kinetics to the number of particles (and therefore
43 as shown in Figure 1. For the initial conditions, he as- their mean size), as predicted by equation (5), has
44 sumes that nucleation begins at the time tm, i.e. that pT(tm) been verified by Sugimoto’s experiments.28-29, 31
45 = 0.28 Equation (3) is linear with constant coefficients, so (ii) While experiments can directly confirm the depend-
∞
46 Sugimoto obtains the number of nuclei as a function of ence of pT on Q, flaws in the derivation of equa-
47 time as
tions (3) – (5) raise questions as to whether the
48 slope actually corresponds to 1/G.
Q
49
50
pT =
G
(1 − exp [ −(t − tm )G / n *]) for t ≥ tm (4) Equation (3) is true at and only at t = tm, but Sugimoto et al.
used and solved equation (3) as though it remains valid for
51 all t ≥ tm. In fact, equation (3) is not a differential equation.
52 The total number of nuclei generated during the burst is It is a condition on the solutions of the coupled differential
53 equations (1) and (2), much like an initial condition. Addi-
54 pT∞ = Q / G (5) tionally, the initial condition invoked by Sugimoto, pT(tm) =
55 0, is incompatible with any nucleation rate expression that
56 where the superscript “∞” indicates a time much longer depends monotonically on supersaturation. For all such
57 than n*/G, but still short compared to the duration of the models, nucleation would begin slightly before tm, climax at
58 growth process. Equation (5) is remarkable because (i) it tm, and then decline toward zero again after tm.
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Here we provide a more rigorous analysis starting from also attained at t = tm. Both Jm and Cm are unknown param-
1 the equations (1) and (2). Clearly, dJ/dt = 0 at t = tm. Thus eters to be determined (or eliminated).
2 equation (3) remains valid, but only as a condition on the J is an increasing function of the concentration C, but we
3 solutions, not as an ordinary differential equation. A se- can also think of J as a function of time (see Figure 1) be-
4 cond condition is required to solve the two coupled first cause C depends on time. Using equation (6) to compute
5 order equations. Differentiating equation (1) again and d2J/dt2 gives
6 using J = dpT/dt gives
7 d 2J dJ
8 2 = −GJ at t = tm (8)
d C dt 2 dC
9 = −G J at t = tm (6)
dt 2
10 J has a strong dependence on concentration. Near the time
11 Now equations (3) and (6) are constraints that must be tm the maximum in C(t) leads to a sharp spike in the nucle-
12 imposed on the solutions of equations (1) and (2). Figure ation rate as depicted in Figure 1. For these reasons (and
13 1 summarizes the equations that describe each portion of for additional reasons described below) the time depend-
14 the LaMer burst nucleation process. ence of J is more difficult to model than that of lnJ. Thus we
15 rewrite equation (8) as
16
17 d2J GJ 2 d ln J
18 = − at t = tm (9)
dt 2 C d ln C
19
20 Nucleation kinetics are somewhat like those of a chemical
21 reaction with high reaction order. For nuclei that form via
22 a sharply defined critical-sized cluster n*, e.g. a transition
23 state between pre- and post-critical magic clusters, one
24 expects a nucleation rate expression of elementary mo-
25 lecular kinetics form, J = kCn*. Such rate expressions yield
26 d ln J / d ln C = n * For nuclei that form via the classical
27 model,33 the nucleation rate expression is J = Aexp[-
28 B/ln2(C/Csat)] where B depends on the temperature, the
29 interfacial free energy, and the nucleus shape. The classi-
30 cal nucleation theory also yields d ln J / d ln C = nm* , as is
31 well-known from the nucleation theorem.34 However, the
32
classical theory predicts nm* = 2 B / ln 3 (C / Csat ) , i.e. the
33
34 critical nucleus size now depends on concentration. For
35 these two nucleation theories and others, a LaMer burst
36 model formulated in terms of dlnJ/dlnC will help to extract
37 the critical nucleus size from experimental data. In all sub-
38 sequent expressions, the postfix |m indicates that the
Figure 1: Each stage of a LaMer burst nucleation process preceeding quantity should be evaluated at the conditions
39 is described by different equations that relate the solute of point t = tm. Also in all subsequent formulas,
40 concentration C, the nucleation rate J, the number of nuclei
41 pT, the growth rate G, and the nucleus size n*. (dlnJ/dlnC)|m will be replaced with nm* .
42 To enable a Laplace’s approximation32 to the total num-
43 ber of nuclei, we model the sharp spike in J(t) as
44 Equations (1) and (2) might be solved using singular
45 perturbation techniques32 because, as depicted in Figure J ≈ J m exp  − 12 (t − t m ) 2 / σ II2  (10)
46 1, C changes over a much longer period than the duration
47 of the nucleation burst which changes pT. However, J and
48 n* are generally complicated and non-linear functions of C. i.e. ln[ J / J m ] = − 12 (t − t m ) 2 / σ II2 where higher order
49 Therefore, the analysis below focuses on general but ap- terms are omitted. To make equation (10) consistent with
proximate consequences of equations (1) and (2).
50
Based on equations (1), (3), and (6), the concentration C equation (9), σ II2 must be defined as
51
52 for times near t = tm is
53 1 GJ m *
≡ nm (11)
54 C = Cm − 12 GJ m (t − tm ) 2 + L (7) σ II2 Cm
55
56 where higher order terms are not shown. Here Cm is the Now 2σ II can be interpreted as the approximate duration
57 maximum concentration which is attained at t = tm, and Jm,
to be determined, is the maximum nucleation rate which is of the nucleation burst. See Figure S1 for a comparison of
58
the classical nucleation theory rate expression with the
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corresponding Gaussian approximation to J(t) in equation solution with a 10-fold excess of KCl solution as a reservoir
1 (10). of Cl- ions. The hydrolysis of diethyl sulfate (DES) in solu-
2 Based on equation (10) the total population of nuclei, tion releases H+ ions which displace Ag+ ions from the gela-
3 ∞ tin into solution. The silver supply rate Q was controlled
pT∞ = ∫ dt J (t ) , is just a Gaussian integral
4 0 by changing the amount of DES that is added to the solu-
5 tion.28 The total number of nuclei was determined from
6 2π Cm J m TEM images of the final nuclei. Figure 2 shows pT∞ vs. Q
7 pT∞ ≈ (12)
8 Gnm* as well as the values of G that are extracted from Sugimo-
to’s analysis and from our analysis. The best fit value of G
9
can be used to confirm that
≪ 1 for all reasonable values
10 Because Jm would be difficult to measure directly, we at-
of nm*, and therefore to confirm the validity of the equation
11 tempt to eliminate it from equation (12). At time t = tm, Jm
12 and pT (tm ) must satisfy Sugimoto’s balance equation: pT∞ = 2Q / G for fitting.
13
14
15
0 = Q − J m nm* − G pT∞ / 2 (13)
16
17 Note that pT (tm ) = pT∞ / 2 according to equation (10).
18
19 Combining (12) and (13) and solving for pT∞ gives
20
21 2Q  1 + 4a − 1 
pT∞ =  
G 
22
2a  (14)
23
24 2Q
25
= (1 − a + L)
G
26
27 where Figure 2: Inferring the growth rate G from the total popu-
28 lation of nuclei and the monomer supply rate Q at the mo-
29 2Q nm* 2 ment of the nucleation burst. The data points are from
30 a≡ ⋅ (15) previous work by Sugimoto et al.28
31 Cm G π
32 PARTICLE SIZE DISTRIBUTIONS
33 The factor Q/CmG within a is expected to be a very small
number. It represents the ratio of the solute supply rate Sugimoto’s equation (4) predicts a sudden onset of nu-
34 cleation with an exponential decaying rate. The corre-
35 divided by the rate of solute consumption if all solutes at
the maximum concentration were separately growing nu- sponding particle size distribution (PSD) would increase
36 exponentially up to a maximum size G(t-tm). Because equa-
37 clei. Equation (14) is a general consequence of equations
(1) and (2). It does not depend on any specific details of tion (4) results in a qualitatively unrealistic PSD, Sugimoto
38 separately used a population balance equation with a nu-
39 the nucleation rate expression. Thus (for sufficiently small
a) our analysis confirms the most remarkable prediction cleation function of cosine shape to model PSDs.8 The co-
40 sine distribution yields a qualitatively realistic PSD, but it
from the work of Sugimoto et al.: the total number of nuclei
41 ispurely empirical. Our extended framework predicts the
is almost entirely controlled by the ratio Q/G, regardless of
42 PSD directly from equations (1) and (2). The population
specific details in the nucleation rate expression.
43 A few differences between our findings and those of density of nuclei of size n at time t’ is
44 Sugimoto should also be noted. First, our analysis predicts
45 t'

46
that large critical nuclei and slow growth kinetics can
p (n, t ') =
∫0
dtJ (t )δ [n(t ' | t ) − n]
(16)
cause non-linear pT∞ vs. Q relationships. The predicted t'
47
48 deviations from linearity may explain results from Hen- ∫ 0
dtJ (t )
49 ∞
dricks et al. who observed a nonlinear p vs. Q relation-
50
T
Here δ is the Dirac delta, and n(t ' | t ) is the size of a nucle-
∞
51 ship. Second, our analysis predicts p = 2Q / G when a is
T us at time t’ given that it was born at an earlier time t. The
52 small, while Sugimoto obtained pT∞ = Q / G . The addi- function n(t ' | t ) is
53
tional factor of two influences the inferred (fitted) growth
54 n(t ' | t ) = n *(t ) + (t '− t )G (17)
rate in the analysis of experimental data.
55 To illustrate that the factor of two in the leading term of
56 equation (14) doubles the inferred growth parameter G, where n*(t) is the critical nucleus size at time t. Particles
57 we reanalyze the AgCl nucleation data of Sugimoto.28 born at each point in time have initial sizes and popula-
58 Sugimoto prepared a gelatin with adsorbed Ag+ ions in tions as indicated by n*(t) and by J(t)dt. After nucleation,
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they are transported along the diagonal lines with slope G the classical nucleation theory (CNT) as an illustrative ex-
1 (characteristics35) to the final time where a schematic of ample. According to CNT, J = Aexp[-B/ln2S] and
2 p(n) is shown. Figure 3 shows how these processes and n* = 2B / ln3 S with S=C/Csat and where A and B are weak
3 the functions n*(t), J(t), and G determine the “final” particle functions of concentration, often taken to be constants. Cm,
4 size distribution p(n). For all times beyond the nucleation G, Q, and pT∞ = 2Q / G can be estimated from experimental
5 pulse, the PSD becomes a wave/bump that travels with a
6 constant shape and constant velocity G. However, at times data like that of Sugimoto et al., but direct estimates of Jm,
7 long after the burst the PSD will also be influenced by rip- nm*, and σII are more elusive. Even if we assume the nucle-
8 ening and aggregation processes that are not included in ation mechanism is classical (it may not be), we cannot
9 our analysis. identify the A and B parameters without Jm, and one of the
10 values nm* or σII.
Fortunately, the PSD contains the required information
11
to identify A and B. The total number of nuclei must satisfy
12
equation (12) and analysis of the PSD with equation (19)
13
provides an additional equation to identify both Jm and σII.
14 A Gaussian approximation to J = Aexp[-B/ln2S] gives
15
16
17  BGJ m 
J ≈ J m exp  − 3
(t − tm ) 2  (20)
18  Cm ln Sm 
19
20 Then using Jm=Aexp[-B/ln2Sm] and 2σII2=Cmln3Sm/(BGJm)
21 from the correspondence between equations (20) and (10)
22 provides equations to find B and A. Figure 4(a) shows
23 how different B-parameters lead to different PSD predic-
24 tions. Figure 4(b) shows how different solute supply
25 rates (Q) with the same B-parameter can be used to tune
Figure 3: As time increases toward tm, the critical nucleus
26 size decreases (black curved arrow), the nucleation rate the PSD.
27 increases (yellow manifold over nucleus size curve), and
28 earliest nuclei to form grow (along the characteristics35 in (a)
29 the (n,t) plane). The nucleation rate reaches a maximum at
30 time tm and then begins to fall. The cumulative number of
31 nuclei generated and carried along each characteristic.
32 gives the PSD p(n). For times after the pulse, the PSD
33 simply travels along the characteristics with no change in
34 shape.
35
36
37 The Supporting Information shows how the integral in
38 equation (16) can be evaluated exactly. The exact PSD
39 expression simplifies considerably under conditions where
40 growth after nucleation is fast ( ≫  ∗/
) and for times
41 t’ after the nucleation burst ( t '− tm ≫ σ II ). Under these
42 conditions the exact PSD approximately simplifies to (b)
43
44 p (n, t ) ≈ J (t ( n)) / GpT∞ (18)
45
46
where t = t(n) is the time at which n*(t’) + G(t-t’) = n. If the
47
critical nuclei are also very small compared to the nucleus
48
sizes at the time of the PSD measurement, then equation
49
(18) further simplifies to
50
51
52 Jm  ( n − G (t − tm )) 2 
p ( n, t ) ≈ ∞
exp  −  (19)
53 GpT  2σ II 2G 2 
54
55 Equations (18) and (19) are important because they
56 Figure 4: (a) The predicted effects of nucleation barrier
relate the PSD to the nucleation function. Given a theoreti-
parameter B on the PSD. (b) The predicted effects of (di-
57 cal nucleation rate expression, they also provide a way to
mensionless) solute supply rate Q/GCsat on the PSD. All
58 extract its kinetic parameters from PSD data. Let us take
PSDs are shown at a time tm + 3σII.
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ly be size independent. In future work, we will develop

1 deterministic models that include size- and concentration-
2 Faster solute supply rates lead to a narrower PSD be- dependent growth kinetics,26-27 and stochastic population
3 cause fewer nuclei are accumulated during the rapid ap- balance models24-25 that self-consistently match the growth
4 proach to (and retreat from) the metastable zone limit. and nucleation fluxes as done in studies of other nucleation
5 The reduced number of nuclei created en route to and from and growth phenomena.36-37 Finally, we note that PSD
6 tm means fewer early and late nuclei which ultimately form predictions at times long after the primary nucleation
7 the large and small tails of the distribution. Note that a burst will require additional models of ripening38 and ag-
8 faster solute supply rate also favors attainment of a slightly gregation.39-40
9 higher value of Sm, a subtle but evident aspect of Sugimo-
10 to’s AgCl and AgBr results. ASSOCIATED CONTENT
11 Larger B-parameters indicate a nucleation rate that is
Supporting information
12 more sharply increasing with supersaturation. When the
B-parameter increases, the nucleation rate more rapidly The Supporting Information is available free of charge on
13 the ACS Publications website at DOE: 10.1021/jacs.XXXXX
skyrockets upward from zero and thereby more sharply
14
focuses the pulse of nucleation events. Integration of equation (16) to obtain the PSD
15
Finally note that the PSDs in Figure 4 were obtained by Accuracy of the Gaussian approximation to J(t)
16
using illustrative B-parameters in the range 16 ≤ B ≤ 64
17
with G, Q, and Csat values from the AgCl experiments of
18 Sugimoto et al. The resulting PSDs are millions of atoms AUTHOR INFORMATION
19 wide, but by the time the particles reach 100nm in radius Corresponding author *baronp@engineering.ucsb.edu
20 they contain ca. 100 million AgCl units. If G is truly size-
21 and concentration-independent, the distribution of sizes
22 would still be ca. 1 million AgCl units wide, making the ACKNOWLEDGMENTS
23 polydispersity extremely small. In reality, we expect the Peters was supported by the U.S. Department of Energy,
24 size- and concentration-dependence of growth as well as Basic Energy Sciences, under grant DE-FG02-03ER15467.
25 aggregation and ripening processes to alter conclusions Chu was supported by a UC LEADS fellowship for under-
26 about the long term size distributions. graduate research at Santa Barbara. Owen was supported
27 by a grant from the National Science Foundation NSF-CHE-
28 CONCLUSIONS 1710352. We thank Colin Unger, Susannah Scott, Linmin
29 Wang, and Bryan Goldsmith for stimulating discussions.
Sugimoto et al. predicted that the number of nuclei gen-
30
erated ( pT∞ ) during a LaMer burst depends only on the
31 REFERENCES
32 solute supply rate (Q) and the growth rate (G). Specifically,
Sugimoto et al. predicted that pT∞ = Q / G , independent of 1. Sear, R., Non-Self-Averaging Nucleation Rate
33
Due to Quenched Disorder. J. Phys. Cond. Matt. 2011, 24,
34 the nucleation kinetics. The prediction that Q controls the 052205.
35 number of nuclei has been verified by some experiments, 2. Agarwal, V.; Peters, B., Solute Precipitate
36 but the roles of growth and nucleation kinetics remain Nucleation: A Review of Theory and Simulation Advances.
37 uncertain because of flaws in the original theoretical anal- Adv. Chem. Phys. 2014, 155, 97-160.
38 ysis. In this work, a more rigorous analysis of the coupled
3. LaMer, V. K., Nucleation in Phase Transitions.
39 equations that govern of the concentrations of solutes and
Ind. Eng. Chem. 1952, 44, 1270-77.
40 nuclei yields a modified prediction for pT∞ . Specifically, we 4. LaMer, V. K.; Dinegar, R. H., Theory, Production,
41 find that pT∞ does depend on the nucleation kinetics, but and Mechanism of Formation of Monodispersed Hydrosols.
42 J. Am. Chem. Soc. 1950, 72, 4847-54.
43 that small nuclei and fast growth rates lead to the limiting
expression pT∞ = 2Q / G , a result that confirms the limited 5. Gebauer, D.; Volkel, A.; Colfen, H., Stable
44 Prenucleation Calcium Carbonate Clusters. Science 2008,
45 role of the nucleation kinetics. 322, 1819-22.
46 The nucleation kinetics have a more pronounced effect 6. Sun, Y., Controlled Synthesis of Colloidal Silver
47 on other aspects of the LaMer burst process. In particular, Nanoparticles in Organic Solutions: Empirical Rules for
48 the nucleation kinetics determine the time and supersatu- Nucleation Engineering. Chem. Soc. Rev. 2013, 42, 2497-
49 ration at the nucleation burst. Moreover, we show that the
511.
50 particle size distributions (PSDs) directly reflect the nucle-
7. Baronov, A.; Bufkin, K.; Shaw, D. W.; Johnson,
51 ation kinetics. Given a PSD shortly after the nucleation
B. L.; Patrick, D. L., A Simple Model of Burst Nucleation.
52 burst, it should be possible to estimate the nucleation ki-
Phys. Chem. Chem. Phys. 2015, 17, 20846-52.
53 netics as a function of time during the nucleation stage.
These results, in combination with experimental LaMer
8. Sugimoto, T., Monodispersed Particles. Elsevier:
54 Amsterdam, 2001.
burst nucleation data, suggest new tests for theories of
55 9. Kwon, S. G.; Hyeon, T., Colloidal Chemical
homogeneous nucleation kinetics.
56 We note that certain assumptions in equations (1) and Synthesis and Formation Kinetics of Uniformly Sized
57 (2) facilitate analysis, but also limit the accuracy of our Nanocrystals of Metals, Oxides, and Chalcogenides. Acc.
58 predictions. In particular, the growth rate G cannot actual- Chem. Res. 2008, 41, 1696-709.
59
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Page 7 of 14 The Journal of Physical Chemistry

10. Sugimoto, T., Preparation of Monodispersed 24. Robb, D. T.; Privman, V., Model of Nanocrystal
1 Colloidal Particles. Adv. Colloid Interface Sci. 1987, 28, Formation in Solution by Burst Nucleation and Diffusional
2 65-108. Growth. Langmuir 2008, 24, 26-35.
3 11. Cossairt, B. M., Shining Light on Indium 25. Privman, V., Models of Size and Shape Control in
4 Phosphide Quantum Dots: Understanding the Interplay Synthesis of Uniform Colloids and Nanocrystals. In Fine
5 among Precursor Conversion, Nucleation, and Growth. Particles in Medicine and Pharmacy, Matijevic, E., Ed.
6 Chem. Mater. 2016, 28, 7181-89. Springer: 2012; pp 1-24.
7 12. Shields, S. P.; Richards, V. N.; Buhro, W. E., 26. Barlow, D. A.; Baird, J. K.; Su, C.-H., Theory of
8 Nucleation Control of Size and Dispersity in Aggregative the von Weimarn Rules Governing the Average Size of
9 Nanoparticle Growth. A Study of the Coarsening Kinetics Crystals Precipitated from a Supersaturated Solution. J.
10 of Thiolate-Capped Gold Nanocrystals. Chem. Mater. Crystal Growth 2004, 264, 417-23.
11 2010, 22, 3212-25. 27. Perala, S. R. K.; Kumar, S., On the Two-Step
12 13. Qiao, L.; Swihart, M. T., Solution-Phase Synthesis Mechanism for Synthesis of Transition Metal
13 of Transition Metal Oxide Nanocrystals: Morphologies, Nanoparticles. Langmuir 2014, 30, 12703-11.
14 Formulae, and Mechanisms. Adv. Colloid Interface Sci. 28. Sugimoto, T.; Shiba, F.; Sekiguchi, T.; Itoh, H.,
15 2017, 244, 199-266. Spontaneous Nucleation of Monodisperse Silver Halide
16 14. Polte, J.; Ahner, T. T.; Delissen, F.; Sokolov, S.; Particles from Homogeneous Gelatin Solution I: Silver
17 Emmerling, F.; Thunemann, A. F.; Kraehnert, R., Chloride. Colloids and Surfaces A: Physicochemical and
18 Mechanism of Gold Nanoparticle Formation in the Engineering Aspects 2000, 164, 183-203.
19 Classical Citrate Synthesis Method Derived from Coupled 29. Sugimoto, T., Underlying Mechanisms in Size
20 In Situ XANES and SAXS Evaluation. J. Am. Chem. Soc. Control of Uniform Nanoparticles. J. Colloid Interface Sci.
21 2010, 132, 1296-301. 2007, 309, 106-18.
22 15. Hendricks, M. P.; Campos, M. P.; Cleveland, G. 30. Zimmermann, N. E. R.; Vorselaars, B.; Quigley,
23 T.; Jen-La Plante, I.; Owen, J. S., A Tunable Library of D.; Peters, B., Nucleation of NaCl from Aqueous Solution:
24 Substituted Thiourea Precursors to Metal Sulfide Critical Sizes, Ion-Attachment Kinetics, and Rates. J. Am.
25 Nanocrystals. Science 2015, 348, 1226-30. Chem. Soc. 2015, 137, 13352-61.
26 16. Volkle, C. M.; Gebauer, D.; Colfen, H., High- 31. Sugimoto, T., The Theory of the Nucleation of
27 Resolution Insights into the Early Stages of Silver Monodisperse Particles in Open Systems and Its
28 Nucleation and Growth. Faraday Discussion 2015, 179, Applications to AgBr Systems. J. Colloid Interface Sci.
29 59-77. 1992, 150, 208-225.
30 17. Campos, M. P.; Hendricks, M. P.; Beecher, A. N.; 32. Bender, C. M.; Orszag, S. A., Advanced
31 Walravens, W.; Swain, R. A.; Cleveland, G. T.; Hens, Z.; Mathematical Methods for Scientists and Engineers: .
32 Sfeir, M. Y.; Owen, J. S., A Library of Selenourea Springer: New York, 1999.
33 Precursors to PbSe Nanocrystals with Size Distributions 33. Kelton, K. F.; Greer, A., Nucleation in Condensed
34 Near the Homogeneous Limit. J. Am. Chem. Soc. 2017, Matter. Elsevier: Amsterdam, 2010.
35 139, 2296-305. 34. Kashchiev, D., Forms and Applications of the
36 18. Yu, W. W.; Peng, X., Formation of High Quality Nucleation Theorem. J. Chem. Phys. 2006, 125, 014502.
37 CdS and Other II-VI Semiconductor Nanocrystals in 35. Rhee, H.-K.; Aris, R.; Amundson, N. R., First-
38 Noncoordinating Solvents: Tunable Reactivity of Order Partial Differential Equations Volume 1: Theory and
39 Monomers. Angew. Chem. Int. Ed. 2002, 41, 2368-71. Applications of Single Equations. Prentice Hall: Englewood
40 19. Owen, J. S.; Chan, E. M.; Liu, H.; Alivisatos, A. Cliffs, NJ, 1986.
41 P., Precursor Conversion Kinetics and the Nucleation of 36. Rempel, J. Y.; Bawendi, M. G.; Jensen, K. F.,
42 Cadmium Selenide Nanocrystals. J. Am. Chem. Soc. 2010, Insights into the Kinetics of Semiconductor Nanocrystal
43 132, 18206-213. Nucleation and Growth. J. Am. Chem. Soc. 2009, 131,
44 20. Boldt, K.; Jander, S.; Hoppe, K.; Weller, H., 4479-89.
Characterization of the Organic Ligand Shell of 37. Vetter, T.; Iggland, M.; Ochsenbein, D. R.;
45
Semiconductor Quantum Dots by Fluorescence Quenching Hänseler, F. S.; Mazzotti, M., Modeling Nucleation,
46
Experiments. ACS Nano 2011, 5, 8115-23. Growth, and Ostwald Ripening in Crystallization
47
21. Shegokar, R.; Muller, R. H., Nanocrystals: Processes: A Comparison between Population Balance and
48
Industrially Feasible Multifunctional Formulation Kinetic Rate Equation. Crystal Growth & Design 2013, 13,
49
Technology for Poorly Soluble Actives. Int. J. 4890-905.
50
Pharmaceutics 2010, 399, 129-139. 38. Lifshitz, I. M.; Slyozov, V. V., The Kinetics of
51
22. Joye, I. J.; McClements, D. J., Production of Precipitation from Supersaturated Solid Solutions. J. Phys.
52
Nanoparticles by Anti-Solvent Precipitation for Use in Chem. Solids 1961, 19, 35-50.
53
Food Systems. Trends in Food Science & Technology 39. Huang, Y.; Pemberton, J. E., Synthesis of
54 2013, 34 (109-123). Uniform, Spherical sub-100nm Silica Particles Using a
55 23. Banfield, J. F.; Welch, S. A.; Zhang, H.; Ebert, T. Conceptual Modification of the Classic La Mer Model.
56 T.; Penn, R. L., Aggregation-Based Crystal Growth and Colloids and Surfaces A: Physicochemical and
57 Microstructure Development in Natural Iron Oxide Engineering Aspects 2010, 360, 175-83.
58 Biomineralization Products. Science 2000, 289, 751-754.
59
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40. Dirksen, J. A.; Benjelloun, S.; Ring, T. A., Colloid and Polymer Sci. 1990, 268, 864-876.
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