Analysis of the Electronic Circular Dichroism Spectrum of (−)–[9](2,5)Pyridinophane

Padula, Daniele; Bari, Lorenzo Di; Santoro, Fabrizio; Gerlach, H.; Rizzo, Antonio

doi:10.1002/chir.22087

Cited by 6 publications

(2 citation statements)

References 79 publications

(170 reference statements)

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“…It is known that the CAMB3LYP functional is a valuable tool for calculating a variety of molecular properties and that it has previously been used with success for the calculation of ECD parameters as well as OR of various compounds (see, e.g., Refs. and references therein). On the other hand, when applied to the simulation of ECD spectra of four rufoolivacins and spiroindolinones, CAM‐B3LYP was shown to be slightly better than B3LYP in the determination of the correct wavelengths and the relative intensity of the electronic transitions.…”

Section: Resultsmentioning

confidence: 99%

Electronic Circular Dichroism of Chiral Alkenes: B3LYP and CAM‐B3LYP Calculations

Jorge

Suave

2014

Chirality

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Time-dependent density functional theory (TDDFT) calculations of electronic circular dichroism (ECD) are widely used to determine absolute configurations (ACs) of chiral molecules. Two very popular DFT exchange-correlation functionals, one hybrid (B3LYP) and one long-range corrected (CAM-B3LYP), along with a hierarchical sequence of basis sets were investigated, and the ECD spectra predicted for eight alkenes and compared to gas-phase experimental spectra. Little variation in predicted ECD spectra was found with the basis set size enlargement, but the sensitivity to the functional is greater. Good agreement was obtained only with the CAM-B3LYP functional, leading to the conclusion that TDDFT calculations of ECD spectra can routinely provide reliable ACs if and only if an appropriate functional is used. For camphene, twistene, syn-(E)-bisfenchylidene, and phyllocladene, solvent effects were estimated.

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Section: Resultsmentioning

confidence: 99%

Electronic Circular Dichroism of Chiral Alkenes: B3LYP and CAM‐B3LYP Calculations

Jorge

Suave

2014

Chirality

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“…Starting from the same assumptions (harmonic approximation, same frequencies and normal modes in both electronic states), it is possible to use the so-called “vertical gradient” (VG) approximation, , which allows the approximation of the full excited state PES from a single gradient calculation at the Franck–Condon point of the ground state equilibrium geometry. The method, also known with the names “linear coupling model” (LCM) or “vertical Franck–Condon” (VFC), has been widely applied − and is particularly useful for molecules for which a geometry optimization in the excited state is either difficult or computationally unfeasible . Within the harmonic approximation we can write the electronic ground state (GS) PES as , where Q GS is the vector of ground state normal modes (expressed in mass-weighted coordinates), and Ω GS is the diagonal matrix of ground state vibrational frequencies.…”

Section: Resultsmentioning

confidence: 99%

Chromophore-Dependent Intramolecular Exciton–Vibrational Coupling in the FMO Complex: Quantification and Importance for Exciton Dynamics

et al. 2017

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In this paper, we adopt an approach suitable for monitoring the time evolution of the intramolecular contribution to the spectral density of a set of identical chromophores embedded in their respective environments. We apply the proposed method to the Fenna-Matthews-Olson (FMO) complex, with the objective to quantify the differences among site-dependent spectral densities and the impact of such differences on the exciton dynamics of the system. Our approach takes advantage of the vertical gradient approximation to reduce the computational demands of the normal modes analysis. We show that the region of the spectral density that is believed to strongly influence the exciton dynamics changes significantly in the timescale of tens of nanoseconds. We then studied the impact of the intramolecular vibrations on the exciton dynamics by considering a model of FMO in a vibronic basis and neglecting the interaction with the environment to isolate the role of the intramolecular exciton-vibration coupling. In agreement with the assumptions in the literature, we demonstrate that high frequency modes at energy much larger than the excitonic energy splitting have negligible influence on exciton dynamics despite the large exciton-vibration coupling. We also find that the impact of including the site-dependent spectral densities on exciton dynamics is not very significant, indicating that it may be acceptable to apply the same spectral density on all sites. However, care needs to be taken for the description of the exciton-vibrational coupling in the low frequency part of intramolecular modes because exciton dynamics is more susceptible to low frequency modes despite their small Huang-Rhys factors.

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Comparison of different synthetic approaches for the fabrication of a bio-inspired 1D-coordination polymer: From solution chemistry to mechanochemistry

Gazzurelli

Solzi

Cugini

et al. 2022

Inorganica Chimica Acta

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Analysis of the Electronic Circular Dichroism Spectrum of (−)–[9](2,5)Pyridinophane

Cited by 6 publications

References 79 publications

Electronic Circular Dichroism of Chiral Alkenes: B3LYP and CAM‐B3LYP Calculations

Electronic Circular Dichroism of Chiral Alkenes: B3LYP and CAM‐B3LYP Calculations

Chromophore-Dependent Intramolecular Exciton–Vibrational Coupling in the FMO Complex: Quantification and Importance for Exciton Dynamics

Comparison of different synthetic approaches for the fabrication of a bio-inspired 1D-coordination polymer: From solution chemistry to mechanochemistry

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