Chiral transition-metal complexes are of interest in many fields ranging from asymmetric catalysis and molecular materials science to optoelectronic applications or fundamental physics including parity violation effects. We present here a combined theoretical and experimental investigation of gas-phase valence-shell photoelectron circular dichroism (PECD) on the challenging open-shell ruthenium( iii )-tris-(acetylacetonato) complex, Ru(acac) 3 . Enantiomerically pure Δ- or Λ-Ru(acac) 3 , characterized by electronic circular dichroism (ECD), were vaporized and adiabatically expanded to produce a supersonic beam and photoionized by circularly-polarized VUV light from the DESIRS beamline at Synchrotron SOLEIL. Photoelectron spectroscopy (PES) and PECD experiments were conducted using a double imaging electron/ion coincidence spectrometer, and compared to density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. The open-shell character of Ru(acac) 3 , which is not taken into account in our DFT approach, is expected to give rise to a wide multiplet structure, which is not resolved in our PES signals but whose presence might be inferred from the additional striking features observed in the PECD curves. Nevertheless, the DFT-based assignment of the electronic bands leads to the characterisation of the ionized orbitals. In line with other recent works, the results confirm that PECD persists independently on the localization and/or on the achiral or chiral nature of the initial orbital, but is rather a probe of the molecular potential as a whole. Overall, the measured PECD signals on Ru(acac) 3 , a system exhibiting D 3 propeller-type chirality, are of similar magnitude compared to those on asymmetric-carbon-based chiral organic molecules which constitute the vast majority of species investigated so far, thus suggesting that PECD is a universal mechanism, inherent to any type of chirality.
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Simulation of Vacuum Ultraviolet Absorption Spectra: Paraffin, Isoparaffin, Olefin, Naphthene, and Aromatic Hydrocarbon Class Compounds
The advent of a new vacuum ultraviolet (VUV) spectroscopic absorption detector for gas chromatography has enabled applications in many areas. Theoretical simulations of VUV spectra using computational chemistry can aid the new technique in situations where experimental spectra are unavailable. In this study, VUV spectral simulations of paraffin, isoparaffin, olefin, naphthene, and aromatic (PIONA) compounds using time-dependent density functional theory (TDDFT) methods were investigated. Important factors for the simulations, such as functionals/basis sets and formalism of oscillator strength calculations, were examined and parameters for future PIONA compound simulations were obtained by fitting computational results to experimental spectra. The simulations produced satisfactory correlations between experimental observations and theoretical calculations, and enabled potential analysis applications for complex higher distillate fuels, such as diesel fuel. Further improvement of the methods was proposed.
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- Award ID(s):
- 1634448
- NSF-PAR ID:
- 10196502
- Date Published:
- Journal Name:
- Applied Spectroscopy
- Volume:
- 74
- Issue:
- 1
- ISSN:
- 0003-7028
- Page Range / eLocation ID:
- 72 to 80
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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This article is categorized under:
Structure and Mechanism > Computational Biochemistry and Biophysics
Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods
Molecular and Statistical Mechanics > Free Energy Methods
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1177/0003702819875132
