التفاصيل البيبلوغرافية
العنوان: |
Static and dynamic descriptions of bond breaking/formation: A complementary view? |
المؤلفون: |
Joubert, Laurent, Adamo, Carlo |
المصدر: |
Journal of Chemical Physics; 12/1/2005, Vol. 123 Issue 21, p211103, 4p, 1 Diagram, 3 Graphs |
مصطلحات موضوعية: |
MOLECULAR dynamics, PHYSICAL & theoretical chemistry, SCISSION (Chemistry), DENSITY, WALDEN inversion, CHEMICAL bonds, ATOMS, CHARGE transfer, ELECTRONS, STATICS |
مستخلص: |
Ab initio molecular-dynamic simulations using density-functional theory and the recent atom-centered density-matrix propagation (ADMP) method were used to study the bond breaking and formation for a case-study substitution nucleophilic bimolecular reaction, namely, the Walden inversion. Using the atoms-in-molecule approach, we have performed a detailed analysis to investigate intra- and intermolecular charge transfer along the ADMP trajectory. These results were compared to those obtained considering a static approach, such as the intrinsic reaction path. In particular, the topological properties computed along the dynamic trajectory well evidence a stronger electron exchange tending to spontaneously maximize the rising covalent interaction. Furthermore, their analysis suggests that the bond formation mechanism involves a reactive intermediate with a bonding interaction stronger than in the final product. [ABSTRACT FROM AUTHOR] |
|
Copyright of Journal of Chemical Physics is the property of American Institute of Physics and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) |
قاعدة البيانات: |
Complementary Index |