Abstract
In this chapter electronic structure computational approaches can be used to predict the kinetics of free-radical polymerization reactions and hence the properties of complex polymers. Much effort is spent is detailing how free-energy changes for reactions and reactive transition states in condensed phases can be obtained using standard computational methods, and how these data can be used to drive complex models of reaction kinetics. Emphasis is placed on the need for calculations to attain chemical accuracy (better than 4 kJ mol-1 or 0.1 eV) and so can be used to interpret polymer properties, and various combinations of current density functional and ab initio methods are prescribed to achieve this goal.
| Original language | English |
|---|---|
| Title of host publication | Computational Methods for Large Systems |
| Subtitle of host publication | Electronic Structure Approaches for Biotechnology and Nanotechnology |
| Editors | Jeffrey R. Reimers |
| Place of Publication | Hoboken, New Jersey |
| Publisher | John Wiley & Sons |
| Pages | 435-474 |
| Number of pages | 40 |
| ISBN (Electronic) | 9780470930779 |
| ISBN (Print) | 9780470487884 |
| DOIs | |
| Publication status | Published - 5 Jul 2011 |
| Externally published | Yes |
Keywords
- Computational methods, modeling free-radical polymerization - free-radical reaction kinetics
- Computational quantum chemistry - chemists, and effects of substituents on individual reactions
- Conformational searching method - energy-directed tree search (EDTS), lowest-energy