Theoretical Study of the Effect of Conformational Structures on the Secondary Oxidation Reactions of cis-1，3-Dimethylcyclohexane

doi:10.7503/cjcu20240458

Abstract

Abstract:

In this study， quantum chemistry method of DLPNO-CCSD（T）/CBS//B3LYP/6-311++G（d，p） was applied for low-temperature secondary oxidation reactions of cis-1，3-dimethylcyclohexane， to optimize molecular geometries， compute vibrational frequencies， and refine single point energies of all related reactants， transition states， and products. In this way， the detailed potential energy surfaces for titled reactions were constructed. High pressure limit rate constants of main reaction channels were calculated based on transition state theory. It was shown that side-chain tended to benefit H-transfer channels of hydroperoxy alkylperoxy radicals（OOQOOH）， among which 1，5-H transfer reactions proved of great significance， competing with decomposition channel forming keto-hydroperoxides（KHP） and OH radical. Dihydrogen peroxide radicals［P（OOH）₂］ resulted from H-transfer of OOQOOH radical mainly underwent cyclic ether reactions. The energy barriers of these reactions tended to increase due to side chain. Based on Rice-Ramsperger-Kassel-Marcus/master equation（RRKM/ME） method， the pressure-dependent rate constants were obtained， revealing that the effect of pressure on the rate constants of all above reactions was weak.

Key words: cis-1, 3-Dimethylcyclohexane, Conformational analysis, Secondary oxidation, Hydrogen transfer reaction, Cyclic ether reaction, Rate constant

CLC Number:

O643.1

TrendMD:

SHEN Yuhao, TIAN Zemin, LI Wei, JI Yixuan, YAN Yingwen. Theoretical Study of the Effect of Conformational Structures on the Secondary Oxidation Reactions of cis-1，3-Dimethylcyclohexane[J]. Chem. J. Chinese Universities, 2025, 46(3): 20240458.

Figures/Tables 17

References 46

1	Zhang T.， Sun W.， Wang L.， Ju Y.， Combust. Flame， 2019， 200， 342—353
2	Okada Y.， Miyashita S.， Izumi Y.， Hayakawa Y.， SAE Int. J. Engines， 2014， 7， 584—594
3	Dec J. E.， Pro. Combust. Inst.， 2009， 488， 294—303
4	Splitter D.， Reitz R.， Hanson R.， SAE Int. J. Fuels Lubr.， 2010， 3， 742—756
5	Ju Y.， Combust. Flame， 2017， 178， 61—69
6	Liu D.， Santner J.， Togbé C.， Felsmann D.， Koppmann J.， Lackner A.， Kohse⁃Höinghaus K.， Combust. Flame， 2013， 160（12）， 2654—2668
7	Dong X.， Duan H.， Jia M.， J. Fuel Sci.， 2023， 127—531
8	Bergthorson J. M.， Thomson M. J.， Renew Sustain Energy Rev.， 2015， 42， 1393—1417
9	Tan N. X.， Wang J. B.， Hua X. X.， Li Z. R.， Li X. Y.， Chem. J. Chinese Universities， 2011， 32（8）， 1832—1837
	谈宁馨，王静波，华晓筱，李泽荣，李象远. 高等学校化学学报， 2011， 32（8）， 1832—1837
10	Li Y. L.， Wang J. B.， Li X. Y.， Chem. J. Chinese Universities， 2018， 39（6）， 1212—1220
	李颖丽，王静波，李象远. 高等学校化学学报， 2018， 39（6）， 1212—1220
11	Shang Y.， Li X.， Zhang Z.， Sun R.， Luo S.， Combust. Flame， 2024， 261， 113—320
12	Oleinikov A. D.， Azyazov V. N.， Mebel A. M.， Combust. Flame， 2018， 191， 209—319
13	Ruan S.， Yin J.， Shi Y.， Qin C.， Xu K.， He C.， Hu X.， Zhang L.， Combust. Flame， 2023， 249， 112616
14	Ye L.， Wang D.， Bian H.， Li B.， Gao W.， Bi M.， Combust. Flame， 2021， 227， 95—105
15	Villano S. M.， Huynh L. K.， Carstensen H. H.， Dean A. M.， J. Phys. Chem. A， 2011， 115， 13425—13442
16	Villano S. M.， Huynh L. K.， Carstensen H. H.， Dean A. M.， J. Phys. Chem. A， 2012， 116， 5068—5089
17	Xing L.， Bao J. L.， Wang Z.， Wang X.， Truhlar D. G.， Combust. Flame， 2018， 197， 88—101
18	Xing L.， Bao J. L.， Wang Z.， Wang X.， Truhlar D. G.， J. Am. Chem. Soc.， 2018， 140， 17556—17570
19	Yao Q.， Sun X. H.， Li Z. R.， Chen F. F.， Li X. Y.， J. Phys. Chem. A， 2017， 121， 3001—3018
20	Sarathy S. M.， Farooq A.， Kalghatgi G. T.， Prog. Energy Combust. Sci.， 2018， 65， 67—108
21	Edwards T.， Maurice L. Q.， J. Propul. Power， 2001， 17， 461—466
22	Pitz W. J.， Mueller C. J.， Prog. Energy Combust. Sci.， 2011， 37（3）， 330—350
23	Liu G.， Yan B.， Chen G.， Renew. Sustain. Energy Rev.， 2013， 25， 59—70
24	Balster L. M.， Corporan E.， DeWitt M. J.， Edwards J. T.， Ervin J. S.， Graham J. L.， Lee S. Y.， Pal S.， Phelps D. K.， Rudnick L. R.， Santoro R. J.， Schobert H. H.， Shafer L. M.， Striebich R. C.， West Z. J.， Wilson G. R.， Woodward R.， Zabarnick S.， Fuel Process. Technol.， 2008， 89， 364—378
25	Zhang X.， Yan H.， Zhu L. J.， Li T.， Wang S. R.， Adv. Sustain. Syst.， 2020， 4（10）， 1900136
26	Mao Y.， Wang S.， Wu Z.， Qiu Y.， Yu L.， Ruan C.， Chen F.， Zhu L.， Lu X.， Combust. Flame， 2019， 206， 83—97
27	Yang Y.， Boehman A. L.， Siimmie J. M.， Combust. Flame， 2010， 157， 2357—2368
28	Tian Z.， Li J.， Yan Y.， Chem. Phys. Lett.， 2020， 755， 137784
29	Xing L.， Lian L.， Truhlar D. G.， Combust. Flame， 2021， 231， 111503
30	Yao X. X.， Wang J. B.， Yao Q.， Li Y. Q.， Li Z. R.， Li X. Y.， Combust. Flame， 2019， 204， 176—188
31	Zou J.， Jin H.， Liu D.， Zhang X.， Combust. Flame， 2022， 235， 111550
32	Bian H.， Zhang Z.， Kuang Y.， Li N.， Chem. Phys. Lett.， 2024， 853， 141496
33	Bian H.， Wang Y.， Li J.， Zhao J.， Int. J. Quantum Chem.， 2022， 122， e26890
34	Bian H.， Zhang Y.， Wang Y.， Zhao J.， Ruan X.， Li J.， Int. J. Quantum Chem.， 2021， 121（11）， e26636
35	Ye L.， Zhang L.， Qi F.， Combust. Flame， 2018， 190， 119—132
36	Alecu I. M.， Truhlar D. G.， J. Phys. Chem. A， 2011， 115（13）， 2811—2829
37	Constantinou L.， Gani R.， Aiche J.， 1994， 40（10）， 1697—1710
38	Georgievskii Y.， Miller J. A.， Burke M. P.， Klippenstein S. J.， J. Phys. Chem. A， 2013 117（46）， 12146—12154
39	Yang Y.， Boehman A. L.， Simmie J. M.， Combust. Flame， 2010， 157（12）， 2369—2379
40	Bian H.， Ye L.， Li J.， Sun J.， Liang T.， Zhong W.， Zhao J.， Combust. Flame， 2019， 205， 193—205
41	Zou J.， Li Y.， Ye L.， Jin H.， Combust. Flame， 2022， 235， 111658
42	Zhang H.， Guo J.， Xu P.， Zhang C.， Wang J.， Combust. Flame， 2022， 245， 112307
43	Miyoshi A.， J. Phys. Chem. A， 2011， 115（15）， 3301
44	Serinyel Z.， Herbinet O.， Frottier O.， Dirrenberger P.， Warth V.， Glaude P. A.， Battin⁃Leclerc F.， Combust. Flame， 2013， 160（11）， 2319—2332
45	Silke E. J.， Pitz W. J.， Westbrook C. K.， Ribaucour M.， J. Phys. Chem. A， 2007， 111（19）， 3761—3775
46	Xing L.， Zhang F.， Zhang L.， Proc. Combust. Inst.， 2017， 36（1）， 179—186

Species	Q_vibration	Q_electronic	Q_{translational}	Q_rotational
TS_aaR2eQ8j_Q3j	0.620×10¹⁸	0.200×10¹	0.910×10⁸	0.121×10⁷
TS_eeR2aQ8j_Q3j	0.201×10¹⁹	0.200×10¹	0.910×10⁸	0.120×10⁷
TS_aaR2eQ8j_Q4j	0.426×10¹⁸	0.200×10¹	0.910×10⁸	0.119×10⁷
TS_eeR2aQ8j_Q4j	0.127×10¹⁸	0.200×10¹	0.910×10⁸	0.106×10⁷

Species	Q_vibration	Q_electronic	Q_{translational}	Q_rotational
TS_aaR2eQ8j_Q3j	0.620×10¹⁸	0.200×10¹	0.910×10⁸	0.121×10⁷
TS_eeR2aQ8j_Q3j	0.201×10¹⁹	0.200×10¹	0.910×10⁸	0.120×10⁷
TS_aaR2eQ8j_Q4j	0.426×10¹⁸	0.200×10¹	0.910×10⁸	0.119×10⁷
TS_eeR2aQ8j_Q4j	0.127×10¹⁸	0.200×10¹	0.910×10⁸	0.106×10⁷

Species	p	T/K	A/（cm³·mol^-1·s^-1）	n	E_a/（J·mol^-1）
eeR1aQ3j_ROO=eeR1aQ3j_Q5j	High pressure limit	300—1800	3810.91011	2.233127	91038.6100
eeR1aQ3j_ROO=eeR1aQ3j_Q8j	High pressure limit	300—1800	0.00603018	4.184921	110374.254
aaR2eQ8j_ROO=aaR2eQ8j_Q3j	High pressure limit	300—1800	0.00075039	4.380401	88013.0340
eeR2aQ8j_ROO=eeR2aQ8j_Q4j	High pressure limit	300—1800	511.615286	2.563875	76505.7788
eeR4aQ8j_ROO=eeR4aQ8j_Q2j	High pressure limit	300—1800	482.278753	2.694932	91171.6612
eeR7eQ2j_ROO=eeR7eQ2j_Q6j	High pressure limit	300—1800	106106.155	2.030745	83644.8125
eeR1aQ3j_Q4j=eeR1aQ3j_Q4j_ 3， 4ETH+OH	High pressure limit	300—1800	28615758188	0.55146	34063.5255
aaR2eQ8j_Q5j=aaR2eQ8j_Q5j_ 5， 8ETH+OH	High pressure limit	300—1800	43248373753	0.491631	52072.7251
eeR2aQ8j_Q3j=eeR2aQ8j_Q3j_ 2， 3ETH+OH	High pressure limit	300—1800	2.017×10¹²	0.384468	55228.1305
eeR2aQ8j_Q3j=eeR2aQ8j_Q3j_ 3， 8ETH+OH	High pressure limit	300—1800	4.089×10¹²	0.40081	57004.1967
aaR2eQ8j=aaR2eQ8j_KHP+OH	High pressure limit	300—1800	0.33388960	3.55955587	86321.7713
eeR2aQ8j=eeR2aQ8j_2KHP+OH	High pressure limit	300—1800	8.628519146	3.276908	72540.9786
eeR4aQ8j_Q3j=eeR4aQ8j_Q3j_ 3， 4ETH+OH	High pressure limit	300—1800	1.199×10¹¹	0.68421	48920.7087
eeR4aQ8j_Q3j=eeR4aQ8j_Q3j_ 3， 8ETH+OH	High pressure limit	300—1800	76225583785	0.665072	49742.3208
eeR4aQ8j=eeR4aQ8j_4KHP+OH	High pressure limit	300—1800	0.430188908	3.452753	76366.7445
eeR7eQ2j_Q6j=eeR7eQ2j_Q6j_ 2， 6ETH+OH	High pressure limit	300—1800	1.804×10¹⁴	-0.08062	87319.034
eeR7eQ2j=eeR7eQ2j_Q2j+OH	High pressure limit	300—1800	5.4001959	3.551797	137825.562

Species	p	T/K	A/（cm³·mol^-1·s^-1）	n	E_a/（J·mol^-1）
eeR1aQ3j_ROO=eeR1aQ3j_Q5j	High pressure limit	300—1800	3810.91011	2.233127	91038.6100
eeR1aQ3j_ROO=eeR1aQ3j_Q8j	High pressure limit	300—1800	0.00603018	4.184921	110374.254
aaR2eQ8j_ROO=aaR2eQ8j_Q3j	High pressure limit	300—1800	0.00075039	4.380401	88013.0340
eeR2aQ8j_ROO=eeR2aQ8j_Q4j	High pressure limit	300—1800	511.615286	2.563875	76505.7788
eeR4aQ8j_ROO=eeR4aQ8j_Q2j	High pressure limit	300—1800	482.278753	2.694932	91171.6612
eeR7eQ2j_ROO=eeR7eQ2j_Q6j	High pressure limit	300—1800	106106.155	2.030745	83644.8125
eeR1aQ3j_Q4j=eeR1aQ3j_Q4j_ 3， 4ETH+OH	High pressure limit	300—1800	28615758188	0.55146	34063.5255
aaR2eQ8j_Q5j=aaR2eQ8j_Q5j_ 5， 8ETH+OH	High pressure limit	300—1800	43248373753	0.491631	52072.7251
eeR2aQ8j_Q3j=eeR2aQ8j_Q3j_ 2， 3ETH+OH	High pressure limit	300—1800	2.017×10¹²	0.384468	55228.1305
eeR2aQ8j_Q3j=eeR2aQ8j_Q3j_ 3， 8ETH+OH	High pressure limit	300—1800	4.089×10¹²	0.40081	57004.1967
aaR2eQ8j=aaR2eQ8j_KHP+OH	High pressure limit	300—1800	0.33388960	3.55955587	86321.7713
eeR2aQ8j=eeR2aQ8j_2KHP+OH	High pressure limit	300—1800	8.628519146	3.276908	72540.9786
eeR4aQ8j_Q3j=eeR4aQ8j_Q3j_ 3， 4ETH+OH	High pressure limit	300—1800	1.199×10¹¹	0.68421	48920.7087
eeR4aQ8j_Q3j=eeR4aQ8j_Q3j_ 3， 8ETH+OH	High pressure limit	300—1800	76225583785	0.665072	49742.3208
eeR4aQ8j=eeR4aQ8j_4KHP+OH	High pressure limit	300—1800	0.430188908	3.452753	76366.7445
eeR7eQ2j_Q6j=eeR7eQ2j_Q6j_ 2， 6ETH+OH	High pressure limit	300—1800	1.804×10¹⁴	-0.08062	87319.034
eeR7eQ2j=eeR7eQ2j_Q2j+OH	High pressure limit	300—1800	5.4001959	3.551797	137825.562

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