Journal ArticleDOI
Intrinsic reaction coordinate: Calculation, bifurcation, and automated search
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TLDR
The intrinsic reaction coordinate (IRC) approach has been used extensively in quantum chemical analysis and prediction of the mechanism of chemical reactions as mentioned in this paper, which gives a unique connection from a given transition structure to local minima of the reactant and product sides.Abstract:
The intrinsic reaction coordinate (IRC) approach has been used extensively in quantum chemical analysis and prediction of the mechanism of chemical reactions. The IRC gives a unique connection from a given transition structure to local minima of the reactant and product sides. This allows for easy understanding of complicated multistep mechanisms as a set of simple elementary reaction steps. In this article, three topics concerning the IRC approach are discussed. In the first topic, the first ab initio study of the IRC and a recent development of an IRC calculation algorithm for enzyme reactions are introduced. In the second topic, cases are presented in which dynamical trajectories bifurcate and corresponding IRC connections can be inaccurate. In the third topic, a recent development of an automated reaction path search method and its application to systematic construction of IRC networks are described. Finally, combining these three topics, future perspectives are discussed. © 2014 Wiley Periodicals, Inc.read more
Citations
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Synthetic and Computational Studies on the Thermal and Photochemical Reactions of [NPN]TaMe3 (NPN = PhP(CH2SiMe2NPh)2) and [MesNPN]TaMe3 (MesNPN = PhP(CH2SiMe2N(2,4,6-Me3C6H2))2)
TL;DR: In this paper, the thermolysis of [PhP(CH2SiMe2NPh)2]TaMe3 leads to the elimination of methane and the formation of cyclometalated derivative [PHP(C6H4)]TaMe2, which was characterized by NMR spectroscopy and single crystal X-ray analysis.
Journal ArticleDOI
Coupled Electrocyclization/Prototropic Shift in the Biosynthesis of Crotinsulidane Diterpenoids.
Renan B. Campos,Dean J. Tantillo +1 more
TL;DR: The energetic viability of proposed mechanisms for the formation of the five-membered ring in crotinsulidane diterpenes is assessed using density functional theory calculations.
Journal ArticleDOI
Prediction of High-Yielding Single-Step or Cascade Pericyclic Reactions for the Synthesis of Complex Synthetic Targets.
Tsuyoshi Mita,Hideaki Takano,Hiroki Hayashi,Wataru Kanna,Yu Harabuchi,K. N. Houk,Satoshi Maeda +6 more
TL;DR: In this article, the artificial force induced reaction (AFIR) was applied to trace an input compound back to reasonable starting materials through thermally allowed pericyclic reactions via product-based quantum-chemistry-aided retrosynthetic analysis (QCaRA) without using any a priori experimental knowledge.
Journal ArticleDOI
Photochemically Driven Tandem Process in the Construction of a Biscyclopropylcage from 2,5-Dimethoxy-p-benzoquinone and Terminal Acetylenes.
TL;DR: The whole process occurs with complete selectivity, and only one densely decorated diastereomer is obtained; such a degree of control and substitution makes for a rather powerful and complexity-building process.
Journal ArticleDOI
The trans–cis isomerization of Ni(η2-TEMPO)2: Interconnections and conformational complexity
TL;DR: In this paper, a conformational and fluxional complexity analysis of the trans-cis isomerization of the Ni( η 2 -TEMPO) 2 precursor is presented.
References
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An introduction to the bootstrap
Bradley Efron,Robert Tibshirani +1 more
TL;DR: This article presents bootstrap methods for estimation, using simple arguments, with Minitab macros for implementing these methods, as well as some examples of how these methods could be used for estimation purposes.
Journal ArticleDOI
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
TL;DR: In this article, a modification of the nudged elastic band method for finding minimum energy paths is presented, where one of the images is made to climb up along the elastic band to converge rigorously on the highest saddle point.
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An Introduction to the Bootstrap
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Journal ArticleDOI
An improved algorithm for reaction path following
TL;DR: In this article, a second order algorithm for finding points on a steepest descent path from the transition state of the reactants and products is presented. But the points are optimized so that the segment of the reaction path between any two adjacent points is given by an arc of a circle, and the gradient at each point is tangent to the path.
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