Eben Sy Dy
A density functional analysis on the photoelectronic spectra of Fe-only hydrogenase analogues
Dy, Eben Sy; Kasai, Hideaki; Redshaw, Carl; Pickett, Christopher J.
Authors
Hideaki Kasai
Emeritus Professor Carl Redshaw C.Redshaw@hull.ac.uk
Emeritus Professor
Christopher J. Pickett
Abstract
Density functional theory calculations have been performed on Fe-only hydrogenase analogues compounds [(i-PDT)Fe2(CP)4(CN) 2]2- (compound I) and [Fe2(CC) 4MeSCH2C(Me)-(CH2S)2(CN)]- (compound II). Results using BPW91/6-311+G(d,p) show electron affinity and trends in molecular orbitais consistent with photoelectron spectroscopy data. The HOMO orbitais show familiar Fe-Fe bonding characteristics while the LUMO orbitais show Fe-Fe anti-bonding characteristics. To compare the effects of a second CN versus a terminal sulfur ligand, results for compound I after one electron is removed (compound 1-1e) were compared with those of compound II. It was found that compound I-1e has a much lower HOMO. Mulliken charge analysis also shows that the terminal sulfur has a stronger electron donating effect than a CN ligand. From the standpoint of computational materials design, we therefore think that similarities in electron affinity, 2Fe charge density and HOMO/LUMO characteristics to the biologically present active site should be bases for predicting catalytic activity of Fe-only hydrogenase analogues. © 2007 The Surface Science Society of Japan.
Citation
Dy, E. S., Kasai, H., Redshaw, C., & Pickett, C. J. (2007). A density functional analysis on the photoelectronic spectra of Fe-only hydrogenase analogues. e-Journal of Surface Science and Nanotechnology, 5, 148-151. https://doi.org/10.1380/ejssnt.2007.148
| Journal Article Type | Article |
|---|---|
| Acceptance Date | Dec 17, 2007 |
| Publication Date | Dec 26, 2007 |
| Deposit Date | Jun 8, 2022 |
| Electronic ISSN | 1348-0391 |
| Publisher | The Japan Society of Vacuum and Surface Science |
| Peer Reviewed | Peer Reviewed |
| Volume | 5 |
| Pages | 148-151 |
| DOI | https://doi.org/10.1380/ejssnt.2007.148 |
| Keywords | Density functional calculations, Photoelectron spectroscopy, Catalysis, Hydrogen Molecule, Hydrogenase, Hydrogen Oxidation and Evolution Reaction |
| Public URL | https://hull-repository.worktribe.com/output/3622604 |