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SN2 Reaction: Transition State02:26

SN2 Reaction: Transition State

10.3K
An SN2 reaction of an alkyl halide is a single-step process in which bond formation between the nucleophile and the substrate and bond breaking between the substrate and the halide occurs simultaneously through a transition state without forming an intermediate.
When the nucleophile approaches the electrophilic carbon with its lone pairs, the halide acts as a leaving group and moves away with the electron-pair bonded to the carbon. Dotted partial bonds represent the bonds being formed or broken...
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Energy Diagrams, Transition States, and Intermediates02:13

Energy Diagrams, Transition States, and Intermediates

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Free-energy diagrams, or reaction coordinate diagrams, are graphs showing the energy changes that occur during a chemical reaction. The reaction coordinate represented on the horizontal axis shows how far the reaction has progressed structurally. Positions along the x-axis close to the reactants have structures resembling the reactants, while positions close to the products resemble the products.  Peaks on the energy diagram represent stable structures with measurable lifetimes, while...
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Multi-Step Reactions02:31

Multi-Step Reactions

7.5K
Chemical reactions often occur in a stepwise fashion involving two or more distinct reactions taking place in a sequence. A balanced equation indicates the reacting species and the product species, but it reveals no details about how the reaction occurs at the molecular level. The reaction mechanism (or reaction path) provides details regarding the precise, step-by-step process by which a reaction occurs. Each of the steps in a reaction mechanism is called an elementary reaction. These...
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Cooperative Allosteric Transitions01:58

Cooperative Allosteric Transitions

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The Small x Assumption02:20

The Small x Assumption

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If a reaction has a small equilibrium constant, the equilibrium position favors the reactants. In such reactions, a negligible change in concentration may occur if the initial concentrations of reactants are high and the Kc value is small. In such circumstances, the equilibrium concentration is approximately equal to its initial concentration.  This estimation can be used to simplify the equilibrium calculations by assuming that some equilibrium concentrations are equal to the initial...
47.1K
Rate-Determining Steps03:08

Rate-Determining Steps

33.7K
Relating Reaction Mechanisms
In a multistep reaction mechanism, one of the elementary steps progresses significantly slower than the others. This slowest step is called the rate-limiting step (or rate-determining step). A reaction cannot proceed faster than its slowest step, and hence, the rate-determining step limits the overall reaction rate.
The concept of rate-determining step can be understood from the analogy of a 4-lane freeway with a short-stretch of traffic-bottleneck caused due to...
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Related Experiment Video

Updated: Sep 29, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
08:04

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids

Published on: May 27, 2020

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Higher-order transition state approximation.

Takahito Nakajima1, Kimihiko Hirao1, Bun Chan1

  • 1Computational Molecular Science Research Team, RIKEN Center for Computational Science, 7-1-26 Minatojima-minami, Cyuo-ku, Kobe, Hyogo 650-0047, Japan.

The Journal of Chemical Physics
|March 23, 2022
PubMed
Summary
This summary is machine-generated.

We introduce higher-order transition state approximations for more accurate electronic excitation energy calculations. The third-order generalized transition state (GTS3) method offers a balance of accuracy and computational efficiency.

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Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Theoretical Chemistry

Background:

  • Slater's transition state concept is crucial for calculating excitation energies.
  • Existing methods may have limitations in accuracy or computational cost.

Purpose of the Study:

  • To generalize Slater's transition state concept with higher-order approximations.
  • To evaluate the accuracy and efficiency of these new approximations.

Main Methods:

  • Derivation of systematic higher-order transition state approximations.
  • Numerical validation using Hartree-Fock and Kohn-Sham density functional theory.
  • Calculation of transition energies for core, valence, and charge-transfer excitations.

Main Results:

  • All developed higher-order approximations accurately reproduced delta self-consistent-field results.
  • The third-order generalized transition state (GTS3) approximation shows a favorable accuracy-to-cost ratio.
  • Combining GTS3 with the transition potential scheme yields accurate results cost-effectively.

Conclusions:

  • Higher-order transition state approximations provide accurate electronic excitation energies.
  • GTS3 is a viable and efficient alternative to existing methods.
  • The transition potential scheme enhances the cost-effectiveness of GTS3.