Circularly polarized luminescence spectrum of camphorquinone

Luk, Chun Ka; Richardson, F. S.

doi:10.1021/ja00814a004

Cited by 46 publications

(29 citation statements)

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“…For the CPL spectrum (Fig. ), experimental data were taken from Ref . since the experimental spectrum in Ref .…”

Section: Resultsmentioning

confidence: 99%

“…In CPL spectroscopy the sample is irradiated with a nonpolarized light and the difference between the number of emitted photons with left‐handed polarization and those with right‐handed polarization is measured. The theoretical foundation of CPL spectroscopy has been widely discussed . Emeis and Oosterhoff, in their pioneering studies, established that both ECD and CPL transitions depend on the rotational strength, which is defined as

{sans-serif-italicR}_{sans-serif-italicmn} = {bold-italicμ}_{sans-serif-italicmn} \cdot ℑ (m_{nm})

.…”

Section: Methodsmentioning

confidence: 99%

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New Developments of a Multifrequency Virtual Spectrometer: Stereo‐Electronic, Dynamical, and Environmental Effects on Chiroptical Spectra

2014

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Computational spectroscopy has recently evolved from a field reserved for specialists toward a general tool allowing interpretations and analyses of experimental results. However, the current practice of providing tables of transitions for rigid geometries, possibly tuned by phenomenological broadening, is by far too naive. In order to improve this situation in the last few years we have been developing a general, robust, and user-friendly virtual spectrometer (VS) able to complement experimental studies for complex systems in condensed phases. The VS is based on flexible graphical pre- and postprocessing tools interfaced with general number-crunching software. This last tool is rooted in several electronic structure methodologies (DFT, TD-DFT, post-Hartree-Fock), powerful discrete/continuum models for describing environmental effects, and general vibrational and vibronic models. These last topics are the main focus of this work, which sketches our latest developments related to effective inclusion of anharmonic contributions, together with time-independent and/or time-dependent descriptions of vibronic transitions including Franck-Condon, Herzberg-Teller, and Duschinsky effects. Some test cases are described in some detail with the aim of showing the role of different effects in ruling vibrational (VCD) and electronic (ECD, CPL) chiral spectroscopies.

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“…For the CPL spectrum (Fig. ), experimental data were taken from Ref . since the experimental spectrum in Ref .…”

Section: Resultsmentioning

confidence: 99%

{sans-serif-italicR}_{sans-serif-italicmn} = {bold-italicμ}_{sans-serif-italicmn} \cdot ℑ (m_{nm})

.…”

Section: Methodsmentioning

confidence: 99%

New Developments of a Multifrequency Virtual Spectrometer: Stereo‐Electronic, Dynamical, and Environmental Effects on Chiroptical Spectra

2014

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“…Theoretical spectra for d-camphorquinone calculated with CAM-B3LYP/ TZVP are shown in Figure 1. The experimental spectra [17] were obtained in cyclohexane solution at room temperature. The effects of solution versus gas phase on the CD spectrum of this molecule have been previously studied and indicated possible influences from medium effects.…”

Section: Resultsmentioning

confidence: 99%

“…[29] However, experimental emission and CPL spectra in ethanol have also been reported, and indicated minor solvent effects for this molecule under the experimental conditions. [17] Therefore, solvent effects were not taken into consideration in the calculations.…”

Section: Resultsmentioning

confidence: 99%

“…The approach taken here is based on the method by Santoro et al for computations of FC factors needed to obtain the vibronic fine structure for absorption and emission spectra, with a focus on modeling CPL. Two molecules for which well-resolved CPL spectra have been reported are d-camphorquinone [17] and (S,S)-trans-b-hydrindanone [7] (Scheme 1). The spectral bands in the region of 2-3 eV for camphorquinone and 3.5-6 eV for hydrindanone can be assigned to n!p*-type transitions associated with the carbonyl groups.…”

Section: Introductionmentioning

confidence: 99%

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Calculation of the Vibrationally Resolved, Circularly Polarized Luminescence of d‐Camphorquinone and (S,S)‐trans‐β‐Hydrindanone

Pritchard

Autschbach

2010

ChemPhysChem

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Circularly polarized luminescence (CPL), the differential emission of left- and right-handed circularly polarized light from a molecule, is modeled by using time-dependent density functional theory. Calculations of the CPL spectra for the first electronic excited states of d-camphorquinone and (S,S)-trans-beta-hydrindanone under the Franck-Condon approximation and using various functionals are presented, as well as calculations of absorption, emission, and circular dichroism spectra. The functionals B3LYP, BHLYP, and CAM-B3LYP are employed, along with the TZVP and aug-cc-pVDZ Gaussian-type basis sets. For the lowest-energy transitions, all functionals and basis sets perform comparably, with the long-range-corrected CAM-B3LYP better reproducing the excitation energy of camphorquinone but leading to a blue shift with respect to experiment for hydrindanone. The vibrationally resolved spectra of camphorquinone are very well reproduced in terms of peak location, widths, shapes, and intensities. The spectra of hydrindanone are well reproduced in terms of overall envelope shape and width, as well as the lack of prominent vibrational structure in the emission and CPL spectra. Overall the simulated spectra compare well with experiment, and reproduce the band shapes, emission red shifts, and presence or absence of visible vibrational fine structure.

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