scholarly journals AM1 and PM3 calculations of the potential energy surfaces for hydroxymethyl radical reactions with nitric oxide and nitrogen dioxide

1991 ◽  
Vol 95 (13) ◽  
pp. 5085-5089 ◽  
Author(s):  
Georgia H. Kalkanis ◽  
George C. Shields
Keyword(s):  
Nitric Oxide ◽  
Potential Energy ◽  
Nitrogen Dioxide ◽  
Potential Energy Surfaces ◽  
Radical Reactions ◽  
Pm3 Calculations ◽  
Hydroxymethyl Radical ◽  
Energy Surfaces

REACTION MECHANISM OF THE CCN RADICAL WITH NITROGEN DIOXIDE

2007 ◽  
Vol 06 (04) ◽  
pp. 661-674 ◽  
Author(s):  
LIN JIN ◽  
YI-HONG DING ◽  
JIAN WANG
Keyword(s):  
Reaction Mechanism ◽  
Potential Energy ◽  
Nitrogen Dioxide ◽  
Reaction Mechanisms ◽  
Low Temperatures ◽  
Potential Energy Surfaces ◽  
Transition States ◽  
Energy Surfaces

The complex singlet and triplet potential energy surfaces (PESs) of the [ C 2 N 2 O 2] system are performed at the B3LYP and Gaussian-3//B3LYP levels in order to investigate the possibility of the carbyne radical CCN in removal of nitrogen dioxide. Thirty minimum isomers and 36 transition states are located. Starting from the very energy-rich reactant R CCN + NO 2, the terminal C -attack adduct NCCN ( O ) O (singlet at -48.6 and triplet at -48.1 kcal/mol) is first formed on both singlet and triplet PESs. Subsequently, the singlet NCCN ( O ) O takes an O -transfer to form the intermediate singlet cis- NCC ( O ) NO (-120.1), which can lead to the fragments NCCO + NO (-94.4) without barrier. The simpler evolution of the triplet NCCN ( O ) O is the direct N – O rupture to form the final fragmentation NCCNO + 3 O (-31.0). However, the lower lying products 3 NCNO + CO (-103.3) and NCNCO + 3 O (-86.5) are kinetically much less competitive. All the involved transition states for the generation of NCCO + NO and NCCNO + 3 O lie much lower than the reactants, and it indicates that this reaction can proceed effectively even at low temperatures. We expect that the reaction CCN + NO 2 can play a role in both combustion and interstellar processes. Comparison is made between the CCN + NO 2 and CH + NO 2 reaction mechanisms.

Potential Energy Surfaces of Nitrogen Dioxide for the Ground State

2007 ◽  
Vol 24 (7) ◽  
pp. 1879-1882
Author(s):  
Shao Ju-Xiang ◽  
Zhu Zheng-He ◽  
Cheng Xin-Lu ◽  
Yang Xiang-Dong
Keyword(s):  
Potential Energy ◽  
Nitrogen Dioxide ◽  
Ground State ◽  
Potential Energy Surfaces ◽  
Energy Surfaces

Resolving the Quadruple Bonding Conundrum in C2 Using Insights Derived from Excited State Potential Energy Surfaces: A Molecular Orbital Perspective

2019 ◽  
Author(s):  
Ishita Bhattacharjee ◽  
Debashree Ghosh ◽  
Ankan Paul
Keyword(s):  
Excited State ◽  
Potential Energy ◽  
Molecular Orbital ◽  
High Spin ◽  
Potential Energy Surfaces ◽  
Valence Bond ◽  
Deep Minimum ◽  
State Potential ◽  
Energy Surfaces ◽  
Mo Theory

The question of quadruple bonding in C<sub>2</sub> has emerged as a hot button issue, with opinions sharply divided between the practitioners of Valence Bond (VB) and Molecular Orbital (MO) theory. Here, we have systematically studied the Potential Energy Curves (PECs) of low lying high spin sigma states of C<sub>2</sub>, N<sub>2</sub> and Be<sub>2</sub> and HC≡CH using several MO based techniques such as CASSCF, RASSCF and MRCI. The analyses of the PECs for the<sup> 2S+1</sup>Σ<sub>g/u</sub> (with 2S+1=1,3,5,7,9) states of C<sub>2</sub> and comparisons with those of relevant dimers and the respective wavefunctions were conducted. We contend that unlike in the case of N<sub>2</sub> and HC≡CH, the presence of a deep minimum in the <sup>7</sup>Σ state of C<sub>2</sub> and CN<sup>+</sup> suggest a latent quadruple bonding nature in these two dimers. Hence, we have struck a reconciliatory note between the MO and VB approaches. The evidence provided by us can be experimentally verified, thus providing the window so that the narrative can move beyond theoretical conjectures.

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