Please use this identifier to cite or link to this item:
http://hdl.handle.net/10397/96103
Title: | Toward high-level theoretical studies of large biodiesel molecules : an ONIOM [QCISD(T)/CBS:DFT] study of the reactions between unsaturated methyl esters (CnH2n−1COOCH3) and hydrogen radical | Authors: | Zhang, L Meng, Q Chi, Y Zhang, P |
Issue Date: | 31-May-2018 | Source: | Journal of physical chemistry A, 31 May 2018, v. 122, no. 21, p. 4882-4893 | Abstract: | A two-layer ONIOM[QCISD(T)/CBS:DFT] method was proposed for the high-level single-point energy calculations of large biodiesel molecules and was validated for the hydrogen abstraction reactions of unsaturated methyl esters that are important components of real biodiesel. The reactions under investigation include all the reactions on the potential energy surface of CnH2n-1COOCH3 (n = 2-5, 17) + H, including the hydrogen abstraction, the hydrogen addition, the isomerization (intramolecular hydrogen shift), and the β-scission reactions. By virtue of the introduced concept of chemically active center, a unified specification of chemically active portion for the ONIOM (ONIOM = our own n-layered integrated molecular orbital and molecular mechanics) method was proposed to account for the additional influence of C=C double bond. The predicted energy barriers and heats of reaction by using the ONIOM method are in very good agreement with those obtained by using the widely accepted high-level QCISD(T)/CBS theory, as verified by the computational deviations being less than 0.15 kcal/mol, for almost all the reaction pathways under investigation. The method provides a computationally accurate and affordable approach to combustion chemists for high-level theoretical chemical kinetics of large biodiesel molecules. | Publisher: | American Chemical Society | Journal: | Journal of physical chemistry A | ISSN: | 1089-5639 | DOI: | 10.1021/acs.jpca.8b02327 | Rights: | © 2018 American Chemical Society This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpca.8b02327. |
Appears in Collections: | Journal/Magazine Article |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
Toward_High-Level_Theoretical.pdf | Pre-Published version | 2.18 MB | Adobe PDF | View/Open |
Page views
49
Last Week
2
2
Last month
Citations as of May 19, 2024
Downloads
54
Citations as of May 19, 2024
SCOPUSTM
Citations
18
Citations as of May 16, 2024
WEB OF SCIENCETM
Citations
15
Citations as of May 16, 2024
Google ScholarTM
Check
Altmetric
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.