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Quantum Mechanics Calculations of the Thermodynamically Controlled Coverage and Structure of Alkyl Monolayers on Si(111) Surfaces

Nemanick, E. Joseph and Solares, Santiago D. and Goddard, William A., III and Lewis, Nathan S. (2006) Quantum Mechanics Calculations of the Thermodynamically Controlled Coverage and Structure of Alkyl Monolayers on Si(111) Surfaces. Journal of Physical Chemistry B, 110 (30). pp. 14842-14848. ISSN 1520-6106. doi:10.1021/jp060640+. https://resolver.caltech.edu/CaltechAUTHORS:20170419-102845785

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Abstract

The heat of formation, ΔE, for silicon (111) surfaces terminated with increasing densities of the alkyl groups CH_3- (methyl), C_2H_5- (ethyl), (CH_3)_2CH- (isopropyl), (CH_3)_3C- (tert-butyl), CH_3(CH_2)_5- (hexyl), CH_3(CH_2)_7- (octyl), and C_6H_5- (phenyl) was calculated using quantum mechanics (QM) methods, with unalkylated sites being H-terminated. The free energy, ΔG, for the formation of both Si−C and Si−H bonds from Si−Cl model componds was also calculated using QM, with four separate Si−H formation mechanisms proposed, to give overall ΔG_S values for the formation of alkylated Si(111) surfaces through a two step chlorination/alkylation method. The data are in good agreement with measurements of the packing densities for alkylated surfaces formed through this technique, for Si−H free energies of formation, ΔG_H, corresponding to a reaction mechanism including the elimination of two H atoms and the formation of a C C double bond in either unreacted alkyl Grignard groups or tetrahydrofuran solvent.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp060640+DOIArticle
http://pubs.acs.org/doi/suppl/10.1021/jp060640%2BPublisherSupporting Information
ORCID:
AuthorORCID
Nemanick, E. Joseph0000-0002-4650-6491
Solares, Santiago D.0000-0003-0895-8160
Goddard, William A., III0000-0003-0097-5716
Lewis, Nathan S.0000-0001-5245-0538
Additional Information:© 2006 American Chemical Society. Received: January 30, 2006; In Final Form: April 5, 2006. Publication Date (Web): July 13, 2006. E.J.N. and N.S.L. gratefully acknowledge the NSF, Grant CHE-021358, for support of this work. S.D.S. and W.A.G. thank the Microelectronics Advanced Research Corporation (MARCO) and its Focus Center on NanoEngineered Architectonics (FENA).
Funders:
Funding AgencyGrant Number
NSFCHE-0213589
Microelectronics Advanced Research Corporation (MARCO)UNSPECIFIED
Focus Center on NanoEngineered Architectonics (FENA)UNSPECIFIED
Issue or Number:30
DOI:10.1021/jp060640+
Record Number:CaltechAUTHORS:20170419-102845785
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170419-102845785
Official Citation:Quantum Mechanics Calculations of the Thermodynamically Controlled Coverage and Structure of Alkyl Monolayers on Si(111) Surfaces E. Joseph Nemanick, Santiago D. Solares, William A. Goddard, III, and Nathan S. Lewis The Journal of Physical Chemistry B 2006 110 (30), 14842-14848 DOI: 10.1021/jp060640+
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76677
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:19 Apr 2017 17:40
Last Modified:15 Nov 2021 17:01

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