Chem. J. Chinese Universities ›› 2014, Vol. 35 ›› Issue (5): 1023.doi: 10.7503/cjcu20131295
• Physical Chemistry • Previous Articles Next Articles
Received:
2013-12-30
Online:
2014-05-10
Published:
2014-04-18
Contact:
DING Yihong
E-mail:yhdd@jlu.edu.cn
Supported by:
CLC Number:
TrendMD:
ZHU Weiwei, DING Yihong. Theoretical Studies on the Reaction Pathways of l-CnH(n=5,6)+
l-C5H+O2 | ΔE/(kJ·mol-1) | l-C5H+O2 | ΔE/(kJ·mol-1) | ||||
---|---|---|---|---|---|---|---|
B3LYP/6-311++ G(d,p) | CCSD(T)/ CC-PVTZ | CCSD(T)/CC- PVTZ+ZPVE | B3LYP/6-311++ G(d,p) | CCSD(T)/ CC-PVTZ | CCSD(T)/CC- PVTZ+ZPVE | ||
R | 0 | 0 | 0 | QTS1/2 | -43.9 | ||
1 | -118.4 | -85.0 | -77.8 | TS1/3 | -112.6 | -88.3 | -82.5 |
Q1 | -49.4 | TS3/P2 | -466.6 | -484.6 | -473.3 | ||
2 | -196.3 | -159.0 | -151.5 | TS3/4 | -465.4 | -475.4 | -465.4 |
Q2 | -183.3 | TS4/5 | -490.5 | -497.6 | -491.3 | ||
3 | -552.4 | -581.3 | -565.0 | P1(CO+HC4O) | -632.8 | -614.4 | -608.5 |
4 | -492.6 | -506.8 | -498.4 | P2(CO2+C4H) | -498.4 | -523.1 | -508.9 |
5 | -633.2 | -660.8 | -653.3 | P3(3O+HC5O) | -182.0 | -183.3 | -178.3 |
Table 1 Relative energies of reactant, intermediates, transition states and products for the l-C5H+O2 reaction at the B3LYP/6-311++G(d,p) level and CCSD(T)/CC-PVTZ//B3LYP/6-311++G(d,p)+ ZPVE level
l-C5H+O2 | ΔE/(kJ·mol-1) | l-C5H+O2 | ΔE/(kJ·mol-1) | ||||
---|---|---|---|---|---|---|---|
B3LYP/6-311++ G(d,p) | CCSD(T)/ CC-PVTZ | CCSD(T)/CC- PVTZ+ZPVE | B3LYP/6-311++ G(d,p) | CCSD(T)/ CC-PVTZ | CCSD(T)/CC- PVTZ+ZPVE | ||
R | 0 | 0 | 0 | QTS1/2 | -43.9 | ||
1 | -118.4 | -85.0 | -77.8 | TS1/3 | -112.6 | -88.3 | -82.5 |
Q1 | -49.4 | TS3/P2 | -466.6 | -484.6 | -473.3 | ||
2 | -196.3 | -159.0 | -151.5 | TS3/4 | -465.4 | -475.4 | -465.4 |
Q2 | -183.3 | TS4/5 | -490.5 | -497.6 | -491.3 | ||
3 | -552.4 | -581.3 | -565.0 | P1(CO+HC4O) | -632.8 | -614.4 | -608.5 |
4 | -492.6 | -506.8 | -498.4 | P2(CO2+C4H) | -498.4 | -523.1 | -508.9 |
5 | -633.2 | -660.8 | -653.3 | P3(3O+HC5O) | -182.0 | -183.3 | -178.3 |
l-C6H+O2 | ΔE/(kJ·mol-1) | l-C6H+O2 | ΔE/(kJ·mol-1) | ||||
---|---|---|---|---|---|---|---|
B3LYP/6-311++ G(d,p) | CCSD(T)/ CC-PVTZ | CCSD(T)/CC- PVTZ+ZPVE | B3LYP/6-311++ G(d,p) | CCSD(T)/ CC-PVTZ | CCSD(T)/CC- PVTZ+ZPVE | ||
R | 0 | 0 | 0 | TS2/3 | -190.8 | -225.2 | -218.0 |
1 | -179.1 | -209.3 | -193.3 | TS3/4 | -506.8 | -540.3 | -527.7 |
2 | -198.8 | -230.2 | -219.3 | TS3/P2 | -425.2 | -434.8 | -426.9 |
3 | -508.5 | -543.2 | -529.4 | TS4/P1 | -545.7 | -587.6 | -579.6 |
4 | -583.8 | -620.6 | -604.7 | P1(3O+HC6O) | -604.7 | -584.2 | -581.3 |
TS1/2 | -114.3 | -126.8 | -117.6 | P2(CO2+C5H) | -467.9 | -490.1 | -488.0 |
TS1/P3 | -126.8 | -124.7 | -117.2 | P3(CO+HC5O) | -181.6 | -185.1 | -178.7 |
Table 2 Relative energies of reactant, intermediates, transition states and products for the l-C6H+O2 reaction at the B3LYP/6-311++G(d,p) level and CCSD(T)/ CC-PVTZ//B3LYP/6-311++G(d,p)+ ZPVE level
l-C6H+O2 | ΔE/(kJ·mol-1) | l-C6H+O2 | ΔE/(kJ·mol-1) | ||||
---|---|---|---|---|---|---|---|
B3LYP/6-311++ G(d,p) | CCSD(T)/ CC-PVTZ | CCSD(T)/CC- PVTZ+ZPVE | B3LYP/6-311++ G(d,p) | CCSD(T)/ CC-PVTZ | CCSD(T)/CC- PVTZ+ZPVE | ||
R | 0 | 0 | 0 | TS2/3 | -190.8 | -225.2 | -218.0 |
1 | -179.1 | -209.3 | -193.3 | TS3/4 | -506.8 | -540.3 | -527.7 |
2 | -198.8 | -230.2 | -219.3 | TS3/P2 | -425.2 | -434.8 | -426.9 |
3 | -508.5 | -543.2 | -529.4 | TS4/P1 | -545.7 | -587.6 | -579.6 |
4 | -583.8 | -620.6 | -604.7 | P1(3O+HC6O) | -604.7 | -584.2 | -581.3 |
TS1/2 | -114.3 | -126.8 | -117.6 | P2(CO2+C5H) | -467.9 | -490.1 | -488.0 |
TS1/P3 | -126.8 | -124.7 | -117.2 | P3(CO+HC5O) | -181.6 | -185.1 | -178.7 |
Fig.1 Potential energy surface of l-C5H+O2 reaction at B3LYP/6-311++G(d,p) level and CCSD(T)/CC-PVTZ//B3LYP/6-311++G(d,p)+ZPVE level(square bracket)^Broken line(---) refer to the pathway in doublet state, real line(—) refer to quartet state.
Fig.3 Optimized structures of the reactant, intermediates, transition states and products in the l-C5H+O2 reaction at B3LYP/6-311++G(d,p) level[Bond lengths are in nm; bond angles are in degree]
Fig.4 Optimized structures of the reactant, intermediates, transition states and products in the l-C6H+O2 reaction at B3LYP/6-311++G(d,p) level[Bond lengths are in nm; bond angles are in degree]
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