A calculation of the rotatory strengths of the electron-transfer transitions of the Tris-(1,10-phenanthroline)iron(II) ion

Král, M.; Moscowitz, Albert; Ballhausen, C. J.

doi:10.1007/bf00527467

Cited by 9 publications

(1 citation statement)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Theoretical approaches are very helpful in the assignment and the interpretation of the CD spectra of chiral metal complexes. − Several decades ago, crystal field models were developed to describe the d-to-d transitions at the metal center (see refs , , , , and references therein). The exciton coupling model was applied to excitations occurring within the ligands of chiral metal complexes − and has been instrumental for the assignment of absolute configurations, for instance of tris-phenanthroline and tris-bipyridyl complexes, before single-crystal X-ray structures became available. It is still widely applied.…”

Section: Introductionmentioning

confidence: 99%

Density Functional Calculation of the Electronic Circular Dichroism Spectra of the Transition Metal Complexes [M(phen)₃]²⁺(M = Fe, Ru, Os)

et al. 2005

View full text Add to dashboard Cite

The circular dichroism spectra of the tris-bidentate metal complexes Lambda-[M(phen)3]2+, with M = Fe, Ru, Os and phen = 1,10-tris-phenanthroline, are investigated computationally, employing time-dependent density functional theory. Good agreement with experimental spectra is obtained for Ru and Os. The Lambda-[Os(phen)3]2+ spectrum is analyzed in detail. It is shown how relativistic effects red shift CD bands where the Os 5d-orbital participates to a large extent in the excitations. Further, the participation of the metal in the ligand pi --> pi exciton CD is determined to be of the order of 10%. Though solvent effects can have a noticeable effect on individual transitions and rotatory strengths, they are demonstrated to have only a very small overall effect on the resulting simulated CD spectra. For Lambda-[Fe(phen)3]2+, the results are shown to be rather sensitive to the choice of the applied hybrid and nonhybrid density functionals, and the optimized geometries based thereupon. In particular, the sign pattern of the lower-energy part (up to 33 x 10(3) cm(-1)) of the Lambda-[Fe(phen)3]2+ CD spectrum is difficult to reproduce. Some combinations of functionals and geometries yield good agreement with experiment, but no "best" approach can be devised based on the available results. Possible sources of errors in the spectrum of Lambda-[Fe(phen)3]2+ due to deficiencies in the functionals and the exchange-correlation kernels are investigated.

show abstract

Section: Introductionmentioning

confidence: 99%

Density Functional Calculation of the Electronic Circular Dichroism Spectra of the Transition Metal Complexes [M(phen)₃]²⁺(M = Fe, Ru, Os)

et al. 2005

View full text Add to dashboard Cite

show abstract

Time-Dependent Density Functional Response Theory for Electronic Chiroptical Properties of Chiral Molecules

Autschbach

Nitsch-Velasquez

Rudolph

2010

Electronic and Magnetic Properties of Chiral Molecules and Supramolecular Architectures

136

145

View full text Add to dashboard Cite

Methodology to calculate electronic chiroptical properties from time-dependent density functional theory (TDDFT) is outlined. Applications of TDDFT to computations of electronic circular dichroism, optical rotation, and optical rotatory dispersion are reviewed. Emphasis is put on publications from 2005 to 2010, but much of the older literature is also cited and discussed. The determination of the absolute configuration of chiral molecules by combined measurements and computations is an important application of TDDFT chiroptical methods and discussed in some detail. Raman optical activity (ROA) spectra are obtained from normal-mode derivatives of the optical rotation tensor and other linear response tensors. A few selected (ROA) benchmarks are reviewed.

show abstract

Carl Johan Ballhausen (1926–2010)

Dahl

2011

Molecular Electronic Structures of Transition Metal Complexes I

View full text Add to dashboard Cite

show abstract

A calculation of the rotatory strengths of the electron-transfer transitions of the Tris-(1,10-phenanthroline)iron(II) ion

Cited by 9 publications

References 22 publications

Density Functional Calculation of the Electronic Circular Dichroism Spectra of the Transition Metal Complexes [M(phen)₃]²⁺(M = Fe, Ru, Os)

Density Functional Calculation of the Electronic Circular Dichroism Spectra of the Transition Metal Complexes [M(phen)₃]²⁺(M = Fe, Ru, Os)

Time-Dependent Density Functional Response Theory for Electronic Chiroptical Properties of Chiral Molecules

Carl Johan Ballhausen (1926–2010)

Contact Info

Product

Resources

About

A calculation of the rotatory strengths of the electron-transfer transitions of the Tris-(1,10-phenanthroline)iron(II) ion

Cited by 9 publications

References 22 publications

Density Functional Calculation of the Electronic Circular Dichroism Spectra of the Transition Metal Complexes [M(phen)3]2+(M = Fe, Ru, Os)

Density Functional Calculation of the Electronic Circular Dichroism Spectra of the Transition Metal Complexes [M(phen)3]2+(M = Fe, Ru, Os)

Time-Dependent Density Functional Response Theory for Electronic Chiroptical Properties of Chiral Molecules

Carl Johan Ballhausen (1926–2010)

Contact Info

Product

Resources

About

Density Functional Calculation of the Electronic Circular Dichroism Spectra of the Transition Metal Complexes [M(phen)₃]²⁺(M = Fe, Ru, Os)

Density Functional Calculation of the Electronic Circular Dichroism Spectra of the Transition Metal Complexes [M(phen)₃]²⁺(M = Fe, Ru, Os)