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SN2 Reaction: Transition State02:26

SN2 Reaction: Transition State

10.6K
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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The Small x Assumption02:20

The Small x Assumption

48.0K
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...
48.0K
Energy Diagrams, Transition States, and Intermediates02:13

Energy Diagrams, Transition States, and Intermediates

18.2K
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...
18.2K
Linear Approximation in Time Domain01:21

Linear Approximation in Time Domain

171
Nonlinear systems often require sophisticated approaches for accurate modeling and analysis, with state-space representation being particularly effective. This method is especially useful for systems where variables and parameters vary with time or operating conditions, such as in a simple pendulum or a translational mechanical system with nonlinear springs.
For a simple pendulum with a mass evenly distributed along its length and the center of mass located at half the pendulum's length,...
171
Thermal Sigmatropic Reactions: Overview01:16

Thermal Sigmatropic Reactions: Overview

2.2K
Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in...
2.2K
Cooperative Allosteric Transitions01:58

Cooperative Allosteric Transitions

8.3K
Cooperative allosteric transitions can occur in multimeric proteins, where each subunit of the protein has its own ligand-binding site. When a ligand binds to any of these subunits, it triggers a conformational change that affects the binding sites in the other subunits; this can change the affinity of the other sites for their respective ligands. The ability of the protein to change the shape of its binding site is attributed to the presence of a mix of flexible and stable segments in the...
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Related Experiment Video

Updated: Oct 27, 2025

Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method
05:51

Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method

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An improved Slater's transition state approximation.

Kimihiko Hirao1, Takahito Nakajima2, Bun Chan3

  • 1Fukui Institute for Fundamental Chemistry, Kyoto University, Takano, Nishihiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103, Japan.

The Journal of Chemical Physics
|July 23, 2021
PubMed
Summary
This summary is machine-generated.

Researchers extended Slater's transition state concept to approximate energy differences using orbital energies. This new method accurately reproduces calculations for occupied and valence orbitals, improving core electron binding energies.

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Area of Science:

  • Computational chemistry
  • Quantum chemistry
  • Theoretical chemistry

Background:

  • Slater's transition state (TS) concept approximates energy differences using electronic structure calculations.
  • Accurate calculation of ionization and binding energies is crucial in quantum chemistry.

Purpose of the Study:

  • To extend Slater's transition state concept for approximating energy differences.
  • To validate the extended method using ionization energies of small molecules.
  • To assess the method's accuracy with Hartree-Fock (HF) and Kohn-Sham (KS) theories.

Main Methods:

  • Extended Slater's transition state concept using three orbital energies.
  • Performed calculations using Hartree-Fock (HF) and Kohn-Sham (KS) theories.
  • Utilized B3LYP and LCgau-core-BOP functionals for calculations.
  • Validated the method with ionization energies of H2O, CO, and pyrrole.

Main Results:

  • The extended method accurately reproduces full Delta Self-Consistent Field (SCF) results for HF occupied orbitals and KS valence orbitals.
  • Significant improvement in core electron binding energies was observed for KS core orbitals, despite inherent self-interaction errors.
  • The method demonstrates high accuracy for occupied and valence orbitals across different theoretical frameworks.

Conclusions:

  • The extended transition state method provides an accurate approximation for energy differences, particularly for occupied and valence orbitals.
  • The approach offers conceptual insights into SCF-type orbital theories.
  • While not yet fully practical, the method is a valuable conceptual tool for understanding electronic structure.