Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/79224
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, LD
Meng, QH 
Chi, YC 
Zhang, P 
Issue Date: 2018
Publisher: American Chemical Society
Source: Journal of physical chemistry A, 31 May 2018, v. 122, no. 21, p. 4882-4893 How to cite?
Journal: Journal of physical chemistry A 
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 beta-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.
URI: http://hdl.handle.net/10397/79224
ISSN: 1089-5639
DOI: 10.1021/acs.jpca.8b02327
Appears in Collections:Journal/Magazine Article

Access
View full-text via PolyU eLinks SFX Query
Show full item record

SCOPUSTM   
Citations

1
Last Week
0
Last month
Citations as of Mar 12, 2019

Page view(s)

11
Last Week
1
Last month
Citations as of Mar 19, 2019

Google ScholarTM

Check

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.