Ab Initio Molecular Orbital Calculations of the Potential Energy Surfaces for the N(2D) + CH4Reaction

1998 ◽  
Vol 102 (1) ◽  
pp. 254-259 ◽  
Author(s):  
Yuzuru Kurosaki ◽  
Toshiyuki Takayanagi ◽  
Kei Sato ◽  
Shigeru Tsunashima
Keyword(s):  
Potential Energy ◽  
Ab Initio ◽  
Molecular Orbital ◽  
Potential Energy Surfaces ◽  
Molecular Orbital Calculations ◽  
Energy Surfaces

scholarly journals Quantum Organic Photochemistry. IV. The Photoisomerization of Diimide and Azoalkanes

1973 ◽  
Vol 51 (18) ◽  
pp. 3097-3101 ◽  
Author(s):  
N. Colin Baird ◽  
Jerrald R. Swenson
Keyword(s):  
Potential Energy ◽  
Ab Initio ◽  
Molecular Orbital ◽  
Ground State ◽  
Potential Energy Surfaces ◽  
Plane Motion ◽  
Substituent Group ◽  
Significant Barrier ◽  
Energy Surfaces ◽  
Π State

Potential energy surfaces for the isomerization of diimide and azomethane in the ground, 1(n,π*),3 (n,π*), and 3(π,π*) states have been calculated by ab initio molecular orbital methods. Two mechanisms are considered in detail, the first involving in-plane motion of the substituent group and the second involving twisting about the N—N bond. The first mechanism is preferred for the ground and 3(π,π*) states, whereas the second mechanism is preferred for the (n,π*) states. A significant barrier to rotation is predicted for the 3(π,π*) state. The vibrationally-relaxed (twisted) lowest triplet of diimide is predicted to lie 36 kcal mol−1 above the ground state.

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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