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Title: Comment on "Quantum Nature of the Sign Preference in Ion-Induced Nucleation"

Abstract

A reliable molecular-level treatment of nucleation requires (i) accurate descriptions of the interaction potentials, (ii) a consistent theoretical approach that connects the interaction potential to the nucleation rate, and (iii) appropriate statistical mechanics to evaluate quantities of interest. In a recent PRL Nadykto et al. [1] “attack the fundamental problem of the sign preference by employing a higher level of theory such as quantum mechanics”, where quantum mechanics in this context refers to electronic structure calculations of interaction energies. They concluded that “The strong effect of the chemical nature of the core ion on the conversion of vapor molecules to clusters is essentially quantum in nature, and, thus, systematic accounting for the actual core species is impossible without taking into account the actual electronic structures of the core ions.” The purpose of this Comment is to point out conceptual errors concerning the critical importance of items (ii) and (iii) above and to clarify misrepresentations of our previous work on this topic [2]. Any consistent theory of nucleation must describe the relevant regions of configuration space that govern the kinetics and thermodynamics of cluster formation through evaporation and condensation processes – e.g., Dynamical Nucleation Theory (DNT) [3].

Authors:
; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
909235
Report Number(s):
PNNL-SA-49736
Journal ID: ISSN 0031-9007; PRLTAO; KC0301020; TRN: US200722%%1047
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Review Letters, 98(10):Art.no.109603; Journal Volume: 98; Journal Issue: 10
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; IONS; NUCLEATION; QUANTUM MECHANICS; ION PAIRS

Citation Formats

Kathmann, Shawn M., Schenter, Gregory K., and Garrett, Bruce C.. Comment on "Quantum Nature of the Sign Preference in Ion-Induced Nucleation". United States: N. p., 2007. Web. doi:10.1103/PhysRevLett.98.109603.
Kathmann, Shawn M., Schenter, Gregory K., & Garrett, Bruce C.. Comment on "Quantum Nature of the Sign Preference in Ion-Induced Nucleation". United States. doi:10.1103/PhysRevLett.98.109603.
Kathmann, Shawn M., Schenter, Gregory K., and Garrett, Bruce C.. Fri . "Comment on "Quantum Nature of the Sign Preference in Ion-Induced Nucleation"". United States. doi:10.1103/PhysRevLett.98.109603.
@article{osti_909235,
title = {Comment on "Quantum Nature of the Sign Preference in Ion-Induced Nucleation"},
author = {Kathmann, Shawn M. and Schenter, Gregory K. and Garrett, Bruce C.},
abstractNote = {A reliable molecular-level treatment of nucleation requires (i) accurate descriptions of the interaction potentials, (ii) a consistent theoretical approach that connects the interaction potential to the nucleation rate, and (iii) appropriate statistical mechanics to evaluate quantities of interest. In a recent PRL Nadykto et al. [1] “attack the fundamental problem of the sign preference by employing a higher level of theory such as quantum mechanics”, where quantum mechanics in this context refers to electronic structure calculations of interaction energies. They concluded that “The strong effect of the chemical nature of the core ion on the conversion of vapor molecules to clusters is essentially quantum in nature, and, thus, systematic accounting for the actual core species is impossible without taking into account the actual electronic structures of the core ions.” The purpose of this Comment is to point out conceptual errors concerning the critical importance of items (ii) and (iii) above and to clarify misrepresentations of our previous work on this topic [2]. Any consistent theory of nucleation must describe the relevant regions of configuration space that govern the kinetics and thermodynamics of cluster formation through evaporation and condensation processes – e.g., Dynamical Nucleation Theory (DNT) [3].},
doi = {10.1103/PhysRevLett.98.109603},
journal = {Physical Review Letters, 98(10):Art.no.109603},
number = 10,
volume = 98,
place = {United States},
year = {Fri Mar 09 00:00:00 EST 2007},
month = {Fri Mar 09 00:00:00 EST 2007}
}