Ab initio quantum mechanical calculation of the reaction probability for the Cl- + PH2Cl -%26gt; ClPH2 + Cl- reaction

作者：Farahani Pooria; Lundberg Marcus; Karlsson Hans O^*

来源：Chemical Physics, 2013, 425: 134-140.

DOI：10.1016/j.chemphys.2013.08.011

• Nucleophilic substitution (S(N)2)
• Reaction probability
• Quantum dynamics

The S(N)2 substitution reactions at phosphorus play a key role in organic and biological processes. Quantum molecular dynamics simulations have been performed to study the prototype reaction Cl- | PH2Cl %26gt; ClPH2 | Cl- , using one and two-dimensional models. A potential energy surface, showing an energy well for a transition complex, was generated using ab initio electronic structure calculations. The one-dimensional model is essentially reflection free, whereas the more realistic two-dimensional model displays involved resonance structures in the reaction probability. The reaction rate is almost two orders of magnitude smaller for the two-dimensional compared to the one-dimensional model. Energetic errors in the potential energy surface is estimated to affect the rate by only a factor of two. This shows that for these types of reactions it is more important to increase the dimensionality of the modeling than to increase the accuracy of the electronic structure calculation.

• 出版日期2013-11-8