Theoretical and Experimental Studies on the Mechanism of Norbornadiene Pauson−Khand Cycloadducts Photorearrangement. Is There a Pathway on the Excited Singlet Potential Energy Surface?

2008 ◽  
Vol 130 (50) ◽  
pp. 16898-16907 ◽  
Author(s):  
Santiago Olivella ◽  
Albert Solé ◽  
Agustí Lledó ◽  
Yining Ji ◽  
Xavier Verdaguer ◽  
...  
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Energy Surface ◽  
Experimental Studies ◽  
Excited Singlet ◽  
Singlet Potential Energy Surface

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.

Kinetics of the reaction between hydroxyl and hydroperoxyl on the singlet potential energy surface

1991 ◽  
Vol 95 (18) ◽  
pp. 6784-6792 ◽  
Author(s):  
Carlos Gonzalez ◽  
John Theisen ◽  
Ling Zhu ◽  
H. Bernhard Schlegel ◽  
William L. Hase ◽  
...  
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Energy Surface ◽  
Singlet Potential Energy Surface ◽  
Kinetics Of

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.

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.

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