Theoretical Study of the 1CF2 + 3O2 Reaction on the Singlet Potential Surface

2013 ◽  
Vol 641-642 ◽  
pp. 140-143
Author(s):  
Cong Yun Shi ◽  
Jia Dong Yu ◽  
Xing Zhong Liu ◽  
Yan Yang ◽  
Lin Wu ◽  
...  
Keyword(s):  
Reaction Mechanisms ◽  
Energy Surface ◽  
Theoretical Study ◽  
Potential Surface ◽  
Single Point ◽  
Stationary Points ◽  
Title Reaction ◽  
Surface Survey ◽  
High Temperature Processes ◽  
Singlet Potential Energy Surface

A detailed singlet potential energy surface survey on the 1CF2 + 3O2 reaction is carried out in order to clarify the reaction mechanisms of the singlet difluorocarbene (1CF2) with oxygen (3O2) at the B3LYP/6-311++G(d,p) level. To determine the accurate energies of all stationary points, the QCISD/6-311++G(d,p) single-point calculations are done by using the B3LYP/6-311++G(d,p) optimized geometric structures. The title reaction is important in high temperature processes. Four product channels, P1(F2 + CO2), P2(F2O + CO), P3(2F + CO2) and P4(FCO + FO), have been found in the 1CF2 + 3O2 reaction. P1(F2 + CO2) and P3(2F + CO2) have comparable contributions to the title reaction and they are more favorable than the other two thermodynamically and kinetically.

Theoretical Study of the 1CHCl + 3O2 Reaction

2011 ◽  
Vol 356-360 ◽  
pp. 20-24
Author(s):  
Cong Yun Shi ◽  
Xing Zhong Liu ◽  
Da Xiao Xu ◽  
Zhi Gang Zhan
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Reaction Mechanisms ◽  
Energy Surface ◽  
Theoretical Study ◽  
Singlet Potential Energy Surface

Subscript textIn order to clarify the reaction mechanisms of the singlet monochlorocarbene radical (1 CHCl) with 3O2 on the singlet potential energy surface (PES), a detailed theoretical study was carried out at the B3LYP/6-311++G(d,p) level. It is found that the first step is the formation of the planar adducts HClCOO via a barrierless association in the 1 CHCl +3 O2 reaction, and then some isomerizations and breakages of bonds takSuperscript texte place, producing P1 (HCO + ClO), P2 (CO2 + HCl) and P3 (CO + HOCl). The product channel of P2 (CO2 + HCl) is the most competitive one both kinetically and thermodynamically. P1 (HCO + ClO) is the least favorable.

THEORETICAL MECHANISTIC STUDY ON THE RADICAL-NEUTRAL REACTION OF CH(X2Π) WITH CH2CO

2010 ◽  
Vol 09 (02) ◽  
pp. 423-433 ◽  
Author(s):  
SHA LI ◽  
YANG GAO ◽  
XIU-JUAN JIA ◽  
HAO SUN ◽  
RONG-SHUN WANG ◽  
...  
Keyword(s):  
Potential Energy ◽  
Energy Surface ◽  
Single Point ◽  
Stationary Points ◽  
Mechanistic Study ◽  
Intrinsic Reaction Coordinate ◽  
Title Reaction ◽  
Olefinic Carbon ◽  
Energy Information ◽  
Good Agreement

A theoretical survey on the potential energy surface for the CH (X2Π) + CH2CO reaction has been carried out. The geometries and energies of all stationary points involved in the reaction are calculated at the UB3LYP/6-311+G(d, p) level. And the more accurate energy information is provided by single point calculations at the UCCSD(T)/6-311++G(2d, 2p) level. Relationships of the reactants, transition states, intermediates, and products are confirmed by the intrinsic reaction coordinate (IRC) calculations. Our calculations demonstrate that this reaction is most likely initiated by carbon-to-olefinic carbon attack manners. The results suggest that P1 (C2H3 + CO) is the most important product through two competitive channels R → IM1 → TS1/P1 → P1 (C2H3 + CO) and R → IM1 → TS1/6 → IM6 → TS6/P1 → P1 (C2H3 + CO) . This study presents highlights of the mechanism of the title reaction, which is in good agreement with experimental results.

Theoretical Study of the 1CHBr + 3O2 Reaction

2011 ◽  
Vol 396-398 ◽  
pp. 2438-2442
Author(s):  
Cong Yun Shi ◽  
Zhi Gang Zhan ◽  
Xing Zhong Liu ◽  
Chang Mei Ke ◽  
Zao Sheng Lv
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Energy Surface ◽  
Theoretical Study ◽  
Transition States ◽  
Stationary Points ◽  
Singlet Potential Energy Surface ◽  
Mechanism Of The Reaction

The mechanism of the reaction of the monobromocarbene (1CHBr) with3O2was studied theoretically at the B3LYP/6-311++G(d,p) level on the singlet potential energy surface (PES). All structures of the stationary points (reactants, intermediates, transition states and products) were optimized and their energies were obtained. Three product channels, P1(HCO + BrO), P2(CO2+ HBr) and P3(CO + HOBr), are found. P2(CO2+ HBr) is the most favorable one both kinetically and thermodynamically.

Theoretical Study of the Mechanism of the 1CBr2 + 3O2 Reaction

2011 ◽  
Vol 356-360 ◽  
pp. 31-34
Author(s):  
Cong Yun Shi ◽  
Jiao Zhang ◽  
Xing Zhong Liu
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Reaction Mechanisms ◽  
Energy Surface ◽  
Theoretical Study ◽  
Transition States ◽  
Reaction Coordinate ◽  
Intrinsic Reaction Coordinate ◽  
Singlet Potential Energy Surface

A detailed theoretical study was done in order to clarify the reaction mechanisms of the singlet dibromocarbene (1CBr2) with3O2on the singlet potential energy surface (PES). All the geometries of reactants, intermediates, transition states and products were obtained at the B3LYP/6-311++G(d,p) level. Intrinsic reaction coordinate (IRC) calculations at the same level were carried out to confirm the connections between transition states and intermediates. It is found that the initial adduct Br2COO (Cs) is formed via a barrierless association in the1CBr2+3O2reaction, and then some isomerizations and breakages of bonds take place, generating P1(BrCO + BrO), P2(CO + Br2O), P3(CO2+ Br2) and P4(CO2+ 2Br). P3(CO2+ Br2) is the most competitive channel kinetically and thermodynamically. P4(CO2+ 2Br) is the least favorable one kinetically.

Theoretical investigation on the reaction of HS+ with CH3NH2

2014 ◽  
Vol 68 (1) ◽  
Author(s):  
Li-Li Zhang ◽  
Hui-Ling Liu ◽  
Hao Tang ◽  
Xu-Ri Huang
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Potential Energy Surfaces ◽  
Energy Surface ◽  
The Other ◽  
Stationary Points ◽  
Title Reaction ◽  
Singlet Potential Energy Surface ◽  
Reaction Channels ◽  
Energy Surfaces

AbstractThe singlet and triplet potential energy surfaces for the reaction of HS+ with the simplest primary amine, CH3NH2, were determined at the CCSD(T)/6-311+G(d,p) level using the B3LYP/6-311G(d,p) and QCISD/6-311G(d,p) geometries. All possible reaction channels were explored. The results show that three paths on the singlet potential energy surface and one path on the triplet potential energy surface are competitive. These four feasible paths provide products which are presented in the paper and they are consistent with previous experimental results. On the other hand, the stationary points involved in the most favourable path all lie below those of the reactant and thus the title reaction is expected to be rapid, which is also consistent with the experiment.

scholarly journals A theoretical study on the mechanism of the reaction between azacyclopropenylidene and oxirane

2015 ◽  
Vol 80 (1) ◽  
pp. 53-62
Author(s):  
Ying Jing ◽  
Xiaojun Tan
Keyword(s):  
Energy Surface ◽  
Theoretical Study ◽  
Single Point ◽  
Geometry Optimization ◽  
Vibrational Analysis ◽  
Membered Ring ◽  
Reaction Pathways ◽  
Stationary Points ◽  
Energy Property ◽  
Mechanism Of The Reaction

The reaction mechanism between azacyclopropenylidene and oxirane has been systematically investigated employing the second-order M?ller-Plesset perturbation theory (MP2) method to better understand the azacyclopropenylidene reactivity with three-membered ring compound oxirane. Geometry optimization, vibrational analysis, and energy property for the involved stationary points on the potential energy surface have been calculated. Energies of all the species are also further corrected by CCSD(T)/6-311+G* single-point calculations. Our calculational results show that there are two possible reaction pathways. From the kinetic viewpoint, the first pathway is primary. From the viewpoint of thermodynamics, the second is dominating.

Theoretical study of the Cl(2P) + SiH4 reaction: Global potential energy surface and product pair-correlated distributions. Comparison with experiment.

2021 ◽  
Author(s):  
J. Espinosa-Garcia ◽  
Jose Carlos Corchado
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Energy Surface ◽  
Theoretical Study ◽  
Title Reaction ◽  
Comparison With Experiment ◽  
Explicitly Correlated ◽  
High Level ◽  
First Time ◽  
Product Pair

For the theoretical study of the title reaction, an analytical full-dimensional potential energy surface named PES-2021 was developed for the first time, by fitting high-level explicitly-correlated ab initio data. This...

A theoretical study on the kinetics for ethanol reaction with formyl radical

2021 ◽  
Vol 11 (1) ◽  
pp. 38-43
Author(s):  
Nguyen Trong Nghia ◽  
Nguyen Duc Trung ◽  
Tran Thi Thoa ◽  
Phan Thi Thuy
Keyword(s):  
Free Radical ◽  
Potential Energy ◽  
Potential Energy Surface ◽  
Rate Constant ◽  
Energy Surface ◽  
Theoretical Study ◽  
Single Point ◽  
Renewable Fuels ◽  
Potential Energy Surface Calculation ◽  
Surface Calculation

C2H5OH is one of important renewable fuels. The mechanism for the C2H5OH + HCO reaction has been investigated by a potential energy surface calculation at the B3LYP/aug-cc-pVTZ (optimization) and CCSD(T)/cc-pVTZ (single-point) levels. Our results show that the HCO free radical can abstract the H atoms in the OH group giving CH3CH2O + CH2O or in the CH2 group giving CH3CHOH + CH2O. The rate constant results by TST calculations considering tunneling corrections show that the second pathway is dominate in all the calculation temperature range of 300-2000K.

Theoretical study on the reaction of atomic oxygen with unsymmetrical dimethylhydrazine

2013 ◽  
Vol 91 (5) ◽  
pp. 315-319 ◽  
Author(s):  
Jinmiao Wen ◽  
Yafang Tian ◽  
Hongqing He ◽  
Li Wang
Keyword(s):  
Rate Constants ◽  
Room Temperature ◽  
Theoretical Study ◽  
Single Point ◽  
State Theory ◽  
Stationary Points ◽  
Energy Profiles ◽  
Unsymmetrical Dimethylhydrazine ◽  
Increasing Temperature ◽  
Dynamics Method

A dual-level direct dynamics method is employed to study the reaction mechanism of (CH3)2NNH2 (unsymmetrical dimethylhydrazine) with the oxygen (O) atom. The geometries and frequencies of all the stationary points are optimized at the MPW1K/6-311G (d, p) level, and the energy profiles are further refined by the interpolated single-point energies (ISPE) method at the BMC-CCSD level of theory. The rate constants of the O atom with (CH3)2NNH2 are evaluated over a wide temperature range of 200–2000 K by using the canonical variational transition-state theory (CVT) with the small curvature tunneling correction (SCT). The agreement between the theoretical and experimental rate constants is good around room temperature. The channels of H abstraction from the -NH2 position favor temperatures below 1200 K. With increasing temperature, contributions from other channels should be taken into account. The reactivity of N2H4, CH3NHNH2, and (CH3)2NNH2 toward atomic O is compared to explore the methylation effect.

THEORETICAL STUDY ON THE MECHANISM OF THE REACTION OF Ni(d10 1S) + H2 + CO2 → NiCO + H2O

2005 ◽  
Vol 04 (02) ◽  
pp. 449-459 ◽  
Author(s):  
SONG QIN ◽  
CHANGWEI HU ◽  
HUAQING YANG
Keyword(s):  
Reaction Mechanism ◽  
Potential Energy ◽  
Potential Energy Surface ◽  
Energy Barrier ◽  
Energy Surface ◽  
Theoretical Study ◽  
Bond Cleavage ◽  
Rate Determining Step ◽  
Singlet Potential Energy Surface ◽  
Mechanism Of The Reaction

The detailed singlet potential energy surface (PES) of the reaction of Ni ( d 10 1 S ) + H 2 + CO 2→ NiCO + H2O is investigated at the CCSD(T) /6-311+ G(2d,2p) // B3LYP /6-311+ G(2d,2p) levels in order to explore possible reaction mechanism of CO 2 hydrogenation on Ni center. The calculation predicts that the co-interacted H 2 involved C–O bond cleavage of CO 2 molecule is prior to the dissociation of adsorbed H 2 molecule, and the entire reaction is exothermic by 297.3 kJ/mol with an energy barrier of 137.7 kJ/mol. The rate-determining step (RDS) for the overall reaction is predicted to be the insertion of Ni into the C–O bond of the CO 2 moiety.

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