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Volumn 115, Issue 24, 2011, Pages 6413-6425

Activation energy distributions predicted by dispersive kinetic models for nucleation and denucleation: Anomalous diffusion resulting from quantization

(1)  Skrdla, Peter J a  

a NONE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY DISTRIBUTION; ANOMALOUS DIFFUSION; CARBAMAZEPINE; CONVERSION TIME; CRITICAL NUCLEI; DENUCLEATION; DISPERSIVE KINETICS; HOPPING MECHANISM; KELVIN EQUATION; LOW ENERGIES; MOLECULAR MOTIONS; NUCLEATION KINETICS; PHASE TRANSFORMATION; RATE ENHANCEMENT; REAL WORLD DATA; S-SHAPED; STRETCHED EXPONENTIAL; TIME-DEPENDENT ACTIVATION;

EID: 79959257692     PISSN: 10895639     EISSN: 15205215     Source Type: Journal    
DOI: 10.1021/jp111767c     Document Type: Article
Times cited : (13)

References (83)
  • 20
    • 79959247614 scopus 로고    scopus 로고
    • note
    • As a point of interest, following the authors introduction (21) of the JMAEK model into the current nanoparticle kinetics literature, (22) other workers (21, 23) have also applied it, lending direct support to the use of dispersive kinetic models for those applications. However, because nanocrystal formation, growth, and evolution have been observed experimentally to occur via various mechanisms (see, for example, ref 24), it is critical that the rate-limiting step be identified in each system. In cases where more than one mechanism might be rate-limiting, it is possible to combine various models to obtain adequate fits to the empirical data (qualitatively), but care must be taken so that is not done at the expense of the physical meaningfulness of the (excessive number of) rate parameters. For instance, in a recent work, (25) the author combined both classical solid-state and dispersive kinetic rate equations to put forth a new model that was able to describe the complex profiles of a solid-state conversion that could be either reaction rate-limited or phase transformation rate-limited, or both, depending on the conditions of temperature and humidity investigated. Because the dispersive kinetic models presented in this work, eqs 10 and 18, describe only elementary nucleation and denucleation rate-limited processes, respectively, yet it is known that potential rate-limiting processes involved in nanocrystal formation might also include the aggregation and/or coalescence of smaller particles as well as the longer-term coarsening (Ostwald ripening) of larger particles, the addition of an extra mechanistic step might be warranted in certain cases. The outcome of doing so might be a three-parameter, two-step kinetic model, provided that one of the mechanistic steps is classical and the other is dispersive.
  • 51
    • 14544291957 scopus 로고    scopus 로고
    • In a coarse-grained approach, the activation energy holistically accounts for both the potential and kinetic energy (dynamical) components associated with the rate-limiting step of the conversion
    • Izvekov, S.; Voth, G. A. J. Phys. Chem. B 2005, 109, 2469. In a coarse-grained approach, the activation energy holistically accounts for both the potential and kinetic energy (dynamical) components associated with the rate-limiting step of the conversion
    • (2005) J. Phys. Chem. B , vol.109 , pp. 2469
    • Izvekov, S.1    Voth, G.A.2
  • 54
    • 33750375121 scopus 로고    scopus 로고
    • see also the Supporting Information provided with ref available at
    • Skrdla, P. J. J. Phys. Chem. A 2006, 110, 11494; see also the Supporting Information provided with ref available at http://pubs.acs.org
    • (2006) J. Phys. Chem. A , vol.110 , pp. 11494
    • Skrdla, P.J.1
  • 61
    • 79959191845 scopus 로고    scopus 로고
    • note
    • In dealing with metallic nanocrystal formation kinetics, whereby the aggregation/coalescence of smaller subunits might be rate-limiting in the formation of clusters larger than the initially formed primary particles, as in the presence of a strong reducing agent, (62) Derjaguin-Laundau-Verwey-Overbeek (DLVO) theory (63, 64) might provide a useful potential. (65)
  • 66
    • 79959190825 scopus 로고    scopus 로고
    • The sign of F in eq 25 is consistent with that pertaining to the attractive force of gravity, whereby a gravitational field is typically assigned a negative potential
    • The sign of F in eq 25 is consistent with that pertaining to the attractive force of gravity, whereby a gravitational field is typically assigned a negative potential.
  • 71
    • 79959268583 scopus 로고    scopus 로고
    • Another reason that the author is interested specifically in shell particles stems from the fact that the key source of the t -dependent driving force for nucleation likely originates from the continuously evolving surface potential, as related by eqs 24 and 25
    • Another reason that the author is interested specifically in shell particles stems from the fact that the key source of the t -dependent driving force for nucleation likely originates from the continuously evolving surface potential, as related by eqs 24 and 25.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.