Abstract
An ab initio method for the calculation and analysis of force along the intrinsic reaction coordinate (IRC) is proposed. The force is expressed as a sum of chemically meaningful terms: electrostatic (ES), polarization (PL), exchange (EX), charge transfer (CT), their coupling term (MIX), and the intramolecular deformation force (def). The method has been applied to the model SN2 reaction: CH4+H−→H−+CH4, for which the IRC has become available. Emphasis is placed on the method and the type of results such an analysis yields.
Keywords
SN2 reactionReaction coordinateIntramolecular forcePolarization (electrochemistry)ReactionComputational chemistryAb initioChemistryPhysicsMolecular physicsAtomic physicsClassical mechanicsPhysical chemistryQuantum mechanicsStereochemistry
Affiliated Institutions
Related Publications
The intrinsic reaction coordinate. An <i>a</i> <i>b</i> <i>i</i> <i>n</i> <i>i</i> <i>t</i> <i>i</i> <i>o</i> calculation for HNC→HCN and H−+CH4→CH4+H−
A practical method of calculating the intrinsic reaction coordinate starting at a saddle point is proposed. The method has been used in combination with the analytical evaluatio...
A theoretical model of solvation in continuum anisotropic dielectrics
A new formulation of the polarizable continuum method (PCM) is presented to describe the electrostatic interaction between molecular solutes and anisotropic media (e.g., liquid ...
Analysis of the Pyramidalization of the Peptide Group Nitrogen: Implications for Molecular Mechanics Energy Functions
Pyramidalization at the peptide group nitrogen atom is analyzed using N-methylacetamide (NMA) as a model molecule. Mutually orthogonal peptide CN torsion and NH out-of-plane ben...
<i>Ab initio</i> Force Constant Approach to Phonon Dispersion Relations of Diamond and Graphite
The phonon dispersion relations of diamond and graphite are calculated using an ab initio force constant method. The force constants are calculated via a self-consistent superce...
Peptide free-energy profile is strongly dependent on the force field: Comparison of C96 and AMBER95
The C96 and AMBER95 force fields were compared with small model peptides Ac-(Ala)n-NMe (Ac = CH3CO, NMe = NHCH3, n=2 and 3) in vacuo and in TIP3P water by computing the free-ene...
Publication Info
- Year
- 1977
- Type
- article
- Volume
- 67
- Issue
- 11
- Pages
- 4880-4883
- Citations
- 33
- Access
- Closed
External Links
Social Impact
Altmetric
PlumX Metrics
Social media, news, blog, policy document mentions
Citation Metrics
33
OpenAlex
Cite This
Bhairav D. Joshi,
Keiji Morokuma
(1977).
Force decomposition analysis along reaction coordinate.
The Journal of Chemical Physics
, 67
(11)
, 4880-4883.
https://doi.org/10.1063/1.434668
Identifiers
- DOI
- 10.1063/1.434668