How Should We Calculate Transition State Geometries for Radical Reactions? The Effect of Spin Contamination on the Prediction of Geometries for Open-Shell Saddle Points

2000 ◽  
Vol 104 (3) ◽  
pp. 446-450 ◽  
Author(s):  
Yao-Yuan Chuang ◽  
Elena L. Coitiño ◽  
Donald G. Truhlar
Keyword(s):  
Transition State ◽  
Saddle Points ◽  
Open Shell ◽  
Radical Reactions ◽  
Spin Contamination

Probing the relationship between spin contamination and first hyperpolarizability: Open-shell Möbius anion

2014 ◽  
Vol 114 (11) ◽  
pp. 720-724 ◽  
Author(s):  
Ying Gao ◽  
Hong-Liang Xu ◽  
Rong-Lin Zhong ◽  
Shi-Ling Sun ◽  
Zhong-Min Su
Keyword(s):  
Open Shell ◽  
First Hyperpolarizability ◽  
Spin Contamination ◽  
The Relationship

Transition State and G2Q Analysis of Hydrocarbon Radical Reactions with Cl2

1995 ◽  
Vol 34 (12) ◽  
pp. 4202-4211 ◽  
Author(s):  
Max Markus Tirtowidjojo ◽  
Brenda Thies Colegrove ◽  
Joseph L. Durant
Keyword(s):  
Transition State ◽  
Radical Reactions ◽  
Hydrocarbon Radical

scholarly journals Accurate, Automated Density Functional Theory for Complex Molecules Using On-the-fly Error Correction

2020 ◽  
Author(s):  
Samuel Blau ◽  
Evan Spotte-Smith ◽  
Brandon Wood ◽  
Shyam Dwaraknath ◽  
Kristin Persson
Keyword(s):  
Density Functional Theory ◽  
High Throughput ◽  
Density Functional ◽  
Saddle Points ◽  
Open Shell ◽  
Redox Potentials ◽  
Functional Theory ◽  
Complex Molecules ◽  
Molecular Systems ◽  
Rate Of Failure

High-throughput density functional theory (DFT) has been widely utilized to study a variety of materials and molecular properties. However, its application to complex molecular systems, including those relevant to electrochemical reactivity and decomposition, has been limited by insufficient automation.Here, we report a broadly applicable, automated framework for the accurate and robust DFT calculation of molecules, capable of addressing species relevant to electrochemistry. This framework is specifically designed to study molecules with different charge states, open-shell electronic structure, metal coordination, and implicit solvation. We first identify appropriate levels of theory that avoid calculation failures and accurately predict molecular redox potentials. We then describe our framework, including methods to automatically detect and correct errors and to optimize structures from saddle points to potential energy surface minima. To demonstrate the efficacy of this framework, we examine a case study including over 12,000 calculations of reactive molecular fragments. This framework is able to reduce the rate of failure for DFT calculations from 25.1% to 1.2%, significantly improving the degree of automation possible for high-throughput molecular DFT.

Quantum chemical modelling of reactions in hydrocarbon combustion. Study of the CH4 + O2 reactions

1984 ◽  
Vol 49 (6) ◽  
pp. 1440-1447 ◽  
Author(s):  
Ján Urban ◽  
Viliam Klimo ◽  
Jozef Tiňo
Keyword(s):  
Transition State ◽  
Ab Initio ◽  
Rate Constants ◽  
Quantum Chemical ◽  
Transition State Theory ◽  
Saddle Points ◽  
State Theory ◽  
Relative Probability ◽  
Hydrocarbon Combustion ◽  
Chemical Modelling

The rate constants of two alternative reactions, i.e CH4 + O2 → CH2 + H2O2 and CH4 + O2 → CH3 + HOO have been studied by the ab initio and MINDO/3 methods. A preliminary appreciation of the used methods has been done with a selected set of carbene reactions. The characteristics of minima as well as the saddle points on the corresponding reaction paths of both reactions have been found. The discussion of the relative probability of a pathway of the above-mentioned reactions is based on the rate constants determined by the use of transition state theory.

Sign in / Sign up

Export Citation Format

Share Document