### Resumen

A synchronous, concerted chemical process is rigorously divided by the reaction force F(R), the negative gradient of V(R), into "reactant" and "product" regions which are dominated by structural changes and an intervening "transition" region which is electronically intensive. The reaction force constant κ(R), the second derivative of V(R), is negative throughout the transition region, not just at the nominal transition state, at which κ(R) has a minimum. This is consistent with experimental evidence that there is a transition region, not simply a specific point. We show graphically that significant nonsynchronicity in the process is associated with the development of a maximum of κ(R) in the transition region, which increases as the process becomes more nonsynchronous. (We speculate that for a nonconcerted process this maximum is actually positive.) Thus, κ(R) can serve as an indicator of the level of nonsynchronicity. [Figure not available: see fulltext.]

Idioma original | English |
---|---|

Páginas (desde-hasta) | 4111-4118 |

Número de páginas | 8 |

Publicación | Journal of Molecular Modeling |

Volumen | 19 |

N.º | 10 |

DOI | |

Estado | Published - oct 2013 |

### Huella dactilar

### ASJC Scopus subject areas

- Physical and Theoretical Chemistry
- Computer Science Applications
- Computational Theory and Mathematics
- Catalysis
- Organic Chemistry
- Inorganic Chemistry

### Citar esto

*Journal of Molecular Modeling*,

*19*(10), 4111-4118. https://doi.org/10.1007/s00894-012-1713-8

}

*Journal of Molecular Modeling*, vol. 19, n.º 10, pp. 4111-4118. https://doi.org/10.1007/s00894-012-1713-8

**Perspectives on the reaction force constant.** / Politzer, Peter; Murray, Jane S.; Jaque, Pablo.

Resultado de la investigación: Article

TY - JOUR

T1 - Perspectives on the reaction force constant

AU - Politzer, Peter

AU - Murray, Jane S.

AU - Jaque, Pablo

PY - 2013/10

Y1 - 2013/10

N2 - A synchronous, concerted chemical process is rigorously divided by the reaction force F(R), the negative gradient of V(R), into "reactant" and "product" regions which are dominated by structural changes and an intervening "transition" region which is electronically intensive. The reaction force constant κ(R), the second derivative of V(R), is negative throughout the transition region, not just at the nominal transition state, at which κ(R) has a minimum. This is consistent with experimental evidence that there is a transition region, not simply a specific point. We show graphically that significant nonsynchronicity in the process is associated with the development of a maximum of κ(R) in the transition region, which increases as the process becomes more nonsynchronous. (We speculate that for a nonconcerted process this maximum is actually positive.) Thus, κ(R) can serve as an indicator of the level of nonsynchronicity. [Figure not available: see fulltext.]

AB - A synchronous, concerted chemical process is rigorously divided by the reaction force F(R), the negative gradient of V(R), into "reactant" and "product" regions which are dominated by structural changes and an intervening "transition" region which is electronically intensive. The reaction force constant κ(R), the second derivative of V(R), is negative throughout the transition region, not just at the nominal transition state, at which κ(R) has a minimum. This is consistent with experimental evidence that there is a transition region, not simply a specific point. We show graphically that significant nonsynchronicity in the process is associated with the development of a maximum of κ(R) in the transition region, which increases as the process becomes more nonsynchronous. (We speculate that for a nonconcerted process this maximum is actually positive.) Thus, κ(R) can serve as an indicator of the level of nonsynchronicity. [Figure not available: see fulltext.]

KW - Concertedness

KW - Reaction force

KW - Reaction force constant

KW - Synchronicity of chemical processes

UR - http://www.scopus.com/inward/record.url?scp=84884976101&partnerID=8YFLogxK

U2 - 10.1007/s00894-012-1713-8

DO - 10.1007/s00894-012-1713-8

M3 - Article

C2 - 23288094

AN - SCOPUS:84884976101

VL - 19

SP - 4111

EP - 4118

JO - Journal of Molecular Modeling

JF - Journal of Molecular Modeling

SN - 1610-2940

IS - 10

ER -