DFT Reactivity Descriptors and Catalysis - Vrije Universiteit Brussel
DFT Reactivity Descriptors and Catalysis - Vrije Universiteit Brussel
DFT Reactivity Descriptors and Catalysis - Vrije Universiteit Brussel
You also want an ePaper? Increase the reach of your titles
YUMPU automatically turns print PDFs into web optimized ePapers that Google loves.
A first try: an order of magnitude analysis<br />
Ethlene:<br />
Exp<br />
η = I − A = 12.45eV = 0.458au<br />
≅ ε LUMO - ε HOMO<br />
Confinement: take λ=4 R B = 0.70Å → R=2.80Å<br />
→ ± spherical confinement with radius ≅ 4.0Å<br />
cfr. Zeolite Cavity with diameter of 8Å<br />
∆η<br />
≃ 0.015au<br />
η=0.473au=12.87eV<br />
Increasing hardness<br />
Increasing in hardness: cfr. Particle in a Box<br />
Cube:<br />
1 L↓<br />
En ∼ ⎯⎯→ E<br />
2<br />
n<br />
− En−<br />
1<br />
↑→<br />
L<br />
Influence on wavelength HOMO-LUMO transition<br />
∆λ~ -3 nm<br />
increasing hardness<br />
Effect opposed to “softening upon<br />
confinement” in the literature<br />
Pag.<br />
30-9-2008 43
Change language