First-principles transition-metal catalysis : efficient and accurate approaches for studying enzymatic systems

(cont.) We apply our approach to several paradigmatic systems: spin state splittings and structural properties of Fe2 and other small molecules as well as the addition-elimination reactions of hydrogen and methane on FeO+ to form water and methanol, respectively. We find that errors from common density functionals which are over 1.0 eV are greatly reduced to on average 0.1 eV when the DFT+U approach is implemented as compared against experiment and highly accurate but expensive quantum chemistry. We also improve structural and vibrational properties, ground state spin identification for a given configuration, and qualitative descriptions of reaction mechanism. Thanks to the minimal overhead of our DFT+U approach, we have also studied properties of systems of over one thousand electrons in size: in particular, the spin density profiles of functionalized cobalt porphyrins on a metal slab support and the reaction mechanism of the halogenating non-heme Fe(II) enzyme, SyrB2. Efficient and accurate study of transition metal chemistry paves the way for predictive and targeted design of catalysts that provide unique solutions for green chemistry and optimal harnessing of alternative energy sources.

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Materials Science and Engineering

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2009

Author dc:creator

• Kulik, Heather J

Advisor dc:contributor.advisor

• Nicola Marzari.

• Materials Science and Engineering.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/46389

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/46389