Evolution of the MLCT band following changes in oxidation state for highly coupled mixed valence complexes Benjamin Lear and Malcolm Chisholm 64th International.

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Presentation transcript:

Evolution of the MLCT band following changes in oxidation state for highly coupled mixed valence complexes Benjamin Lear and Malcolm Chisholm 64th International Symposium on Molecular Spectroscopy June 23 rd 2009

Mixed-valence systems and their classification Localized electronic states Non- adiabatic Adiabatic Localized electronic states Class I Free Energy X Delocalized electronic states Class III Free Energy X Class II Free Energy X Solvent dependent IVCT band Solvent independent IVCT band 1+

M M mixed valence complexes

MLCT in neutral vs. mixed valence state IVCT band

A three state model for mixed valence chemistry Symmetric coordinate Asymmetric coordinate Free energy IVCT MLCT

Electronic transitions of the mixed valence state MLCT IVCT 1+ Class III

T1T1 T3T3 T2T2 Frequency Intensity Time Overlap 1/ 2/2/ Fourier Transform Nuclear coordinate

Raman spectra Wavenumber /cm -1 Intensity

MLCT simulation Neutral

PES offsets Nuclear Coordinate 1

Mixed-valence systems and their classification Localized electronic states Non- adiabatic Adiabatic Localized electronic states Class I Free Energy X Delocalized electronic states Class III Free Energy X Class II Free Energy X Solvent dependent IVCT band Solvent independent IVCT band 1+

Symmetric coordinate PES and classification Asymmetric coordinate Symmetric coordinate Class IClass IIClass IIIClass IV

Conclusions MLCT band in mixed valence complexes contains information regarding the underlying states Coupling in mixed valence systems tends to make states more similar to one another

Acknowledgments Malcolm H. Chisholm The Chisholm research group

Classification of mixed valence complexes: The “nesting” criterion View along the symmetric coordinate Class IClass IVClass III

Theories for absorption profiles Time dependent pictureFranck-Condon picture

Three-state model: Orbital picture

Concerning the current models Class IV IVCT MLCT “IVCT” “MLCT” Class I Nuclear coordinate

Conclusions MLCT band in mixed valence complexes contains information regarding the underlying states Coupling in mixed valence systems tends to make states more similar to one another Orbital pictures for describing coupling between states are dangerous ≠