Do Nonplanar Porphyrins Have Red-Shifted Electronic Spectra? A DFT/SCI Study and Reinvestigation of a Recent Proposal

Parusel, Andreas B. J.; Wondimagegn, and Tebikie; Ghosh, Abhik

doi:10.1021/ja000757q

Cited by 147 publications

(148 citation statements)

References 23 publications

Supporting

Mentioning

141

Contrasting

Unclassified

Order By: Relevance

“…It is assumed to be due to a smaller effective p system. [111,116] This interpretation is supported by cyclovoltammetry experiments (see, e.g., ref. [114]).…”

Section: Axial Ligand and Nonplanar Distortion Of The Aromatic Ringmentioning

confidence: 54%

Quantum Chemical Description of Absorption Properties and Excited‐State Processes in Photosynthetic Systems

2011

View full text Add to dashboard Cite

The theoretical description of the initial steps in photosynthesis has gained increasing importance over the past few years. This is caused by more and more structural data becoming available for light-harvesting complexes and reaction centers which form the basis for atomistic calculations and by the progress made in the development of first-principles methods for excited electronic states of large molecules. In this Review, we discuss the advantages and pitfalls of theoretical methods applicable to photosynthetic pigments. Besides methodological aspects of excited-state electronic-structure methods, studies on chlorophyll-type and carotenoid-like molecules are discussed. We also address the concepts of exciton coupling and excitation-energy transfer (EET) and compare the different theoretical methods for the calculation of EET coupling constants. Applications to photosynthetic light-harvesting complexes and reaction centers based on such models are also analyzed.

show abstract

“…It is assumed to be due to a smaller effective p system. [111,116] This interpretation is supported by cyclovoltammetry experiments (see, e.g., ref. [114]).…”

Section: Axial Ligand and Nonplanar Distortion Of The Aromatic Ringmentioning

confidence: 54%

Quantum Chemical Description of Absorption Properties and Excited‐State Processes in Photosynthetic Systems

2011

View full text Add to dashboard Cite

show abstract

“…Therefore, having two forms, short-wavelength form is likely to be planar as predicted in Ref. [27]. Secondly, PdP molecule, as well as other metallocomplexes of porphin in solution at room temperature has planar conformation of the macrocycle [14,28].…”

Section: Interpretation Of the Structural Features For Both Spectral mentioning

confidence: 79%

Observation of the distorted form of Pd-porphin in single site spectra at low temperatures

Старухин

Kruk

Czerwieniec

2008

Journal of Luminescence

View full text Add to dashboard Cite

“…The results of the TDDFT calculations re¯ect not only the shape of the spectrum but also the bathochromic shifts. Thus, benzo [c]thiophene (23) is correctly predicted to be redshifted relative to benzo [b]thiophene (22) and cyclopenta [c]thiopyrane (26) is predicted to be redshifted relative to cyclopenta [b]thiopyran (25). As documented in Gleiter et al [55] performed polarization measurements of 28 in stretched ®lms.…”

Section: Compounds With Dicoordinated and Higher-coordinated Sulfurmentioning

confidence: 82%

“…Fortunately these transitions generally occur only at higher energies. Modi®ed TDDFT methods were put forward, such as TDDFT in the Tamm±Danco approximation [23] and DFT/CIS [24,25] and DFT/ MRCI methods [26], including, in part, few empirical parameters. The more approximate and, therefore, more ecient density functional±tight binding (DFTB)±time-dependent local density approximation (TDLDA) method recently developed [27] makes use of the local density approximation.…”

Section: Regular Articlementioning

confidence: 99%

Electronic excitation of sulfur-organic compounds - performance of time-dependent density functional theory

Fabian

2001

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

184

View full text Add to dashboard Cite

To de®ne the scope and limitations of the time-dependent density functional theory (TDDFT) method, spectral absorption data of a series of about 100 neutral or charged sulfur-organic compounds with up to 24 non-hydrogen atoms and up to four sulfur atoms were calculated in the near-UV, visible and IR regions. Although the theoretical vertical transition energies correspond only approximately to experimental absorption band maxima, the mean absolute deviation was calculated to be 0.21 eV (1600 cm )1 ). The main absorption features of various compounds with monocoordinated or dicoordinated sulfur atoms are well reproduced. As far as possible TDDFT results were compared with those of semiempirical Zerner's intermediate neglect of dierential overlap (ZINDO/S) and of Pariser±Parr±Pople (PPP) calculations. TDDFT also works well in cases where the semiempirical methods fail. Limitations of TDDFT were encountered with calculations of spectral absorptions of dye molecules. The``vinylene shift'' of polymethine dyes is not reproduced by TDDFT. Whereas electronic excitation energies delocalized polar and betainic chromophores are reasonably well reproduced, excitation energies of charge-transfer-type and charge-resonance-type transitions of weakly interacting composite chromophores are signi®cantly underestimated.

show abstract

Do Nonplanar Porphyrins Have Red-Shifted Electronic Spectra? A DFT/SCI Study and Reinvestigation of a Recent Proposal

Cited by 147 publications

References 23 publications

Quantum Chemical Description of Absorption Properties and Excited‐State Processes in Photosynthetic Systems

Quantum Chemical Description of Absorption Properties and Excited‐State Processes in Photosynthetic Systems

Observation of the distorted form of Pd-porphin in single site spectra at low temperatures

Electronic excitation of sulfur-organic compounds - performance of time-dependent density functional theory

Contact Info

Product

Resources

About