| Autor: |
Nance J; Department of Mathematics and ‡Department of Chemistry, North Carolina State University (NCSU) , Raleigh, North Carolina 27695, United States., Bowman DN; Department of Mathematics and ‡Department of Chemistry, North Carolina State University (NCSU) , Raleigh, North Carolina 27695, United States., Mukherjee S; Department of Mathematics and ‡Department of Chemistry, North Carolina State University (NCSU) , Raleigh, North Carolina 27695, United States., Kelley CT; Department of Mathematics and ‡Department of Chemistry, North Carolina State University (NCSU) , Raleigh, North Carolina 27695, United States., Jakubikova E; Department of Mathematics and ‡Department of Chemistry, North Carolina State University (NCSU) , Raleigh, North Carolina 27695, United States. |
| Jazyk: |
angličtina |
| Zdroj: |
Inorganic chemistry [Inorg Chem] 2015 Dec 07; Vol. 54 (23), pp. 11259-68. Date of Electronic Publication: 2015 Nov 16. |
| DOI: |
10.1021/acs.inorgchem.5b01747 |
| Abstrakt: |
Iron(II) polypyridine complexes have the potential for numerous applications on a global scale, such as sensitizers, sensors, and molecular memory. The excited-state properties of these systems, particularly the intersystem crossing (ISC) rates, are sensitive to the choice of ligands and can be significantly altered depending on the coordination environment. We employ density functional theory and Smolyak's sparse grid interpolation algorithm to construct potential energy surfaces (PESs) for the photophysically relevant states ((1)A, (3,5)MC, and (1,3)MLCT) of the [Fe(tpy)2](2+) (tpy = 2,2':6',2"-terpyridine) complex, with the goal of obtaining a deeper understanding of the ground- and excited-state electronic structure of this system. The three dimensions that define our adiabatic PESs consist of equatorial and axial metal-ligand bond length distortions and a terpyridine ligand "rocking angle", which has not previously been investigated. The intersection crossing seams and minimum energy crossing points (MECPs) between surfaces are also determined. Overall, we find that the PESs of all electronic excited states investigated are characterized by low-energy valleys along the tpy rocking-angle coordinate. This results in the presence of large low-energy areas around the MECPs on the intersection seams of different electronic states and indicates that inclusion of this third coordinate is crucial for an adequate description of the PESs and surface crossing seams of the [Fe(tpy)2](2+) complex. Finally, we suggest that tuning the energetics of the tpy ligand rocking motion could provide a way to control the ISC process in this complex. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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