Sensitivity of Photoelectron Angular Distributions to Molecular Conformations of Anions

Anstöter, Cate S.; Dean, Charlie R.; Verlet, Jan R. R.

doi:10.1021/acs.jpclett.7b00726

Cited by 18 publications

(40 citation statements)

References 53 publications

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“…A similar observation has been made for gauche and anti conformers of para-ethyl phenolate anions. 44 For both sets of substituents, resonant autodetachment is found to give rise to parallel or isotropic photoelectron angular distributions, resulting in the measured average β 2 parameters being more positive than the ezDyson predictions in the wavelength range of the resonances.…”

Section: Photoelectron Angular Distributionsmentioning

confidence: 85%

Photoelectron Imaging and Quantum Chemistry Study of Phenolate, Difluorophenolate, and Dimethoxyphenolate Anions

et al. 2019

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Phenolates and their substituted analogues are important molecular motifs in many biological molecules, including the family of fluorescent proteins based on green fluorescent protein. We have used a combination of anion photoelectron velocity-map imaging measurements and quantum chemistry calculations to probe the electronic structure of the phenolate anion and difluoro-and dimethoxy-substituted analogues. We report vertical detachment energies (VDEs) and quantify the photoelectron angular distributions. The VDEs for phenolate (2.26 ± 0.03 eV, 3.22 ± 0.02 eV) are in agreement with high-resolution measurements, whereas the values for the substituted analogues (2.61 ± 0.03 eV for difluorophenolate; ∼ 2.35 eV for dimethoxyphenolate) are new measurements. We also report adiabatic excitation energies (AEEs) of anion resonances and discuss their contributions to the overall photoelectron angular distributions. The AEE of the lowest lying resonance in phenolate (∼ 3.36 eV) is consistent with previous measurements, whereas the value for the next resonance (∼ 3.7 eV) is a new measurement. The AEEs of the resonances in the substituted analogues (∼ 3.74 eV for difluorophenolate; ∼ 3.4 eV and 3.74 eV for dimethoxyphenolate) are new measurements.

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Section: Photoelectron Angular Distributionsmentioning

confidence: 85%

Photoelectron Imaging and Quantum Chemistry Study of Phenolate, Difluorophenolate, and Dimethoxyphenolate Anions

et al. 2019

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“…This variation must be due to electron autodetachment in competition with direct photodetachment, a behavior that has been observed in other aromatic systems. 47,[49][50][51] This conclusion is borne out in excited state quantum chemical calculations (TD-DFT) of the indolide anion which predict 9 optically accessible electronic states with term energies ranging from 2.5 to 3.6 eV above the ground vibronic state energy. Due to the density of the available states and the inherent complexity of autodetachment, it is beyond the scope of this work to further investigate this phenomenon theoretically.…”

Section: Discussionmentioning

confidence: 99%

Anion photoelectron spectroscopy of deprotonated indole and indoline

Nelson

Oliveira

Lineberger

2018

The Journal of Chemical Physics

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Anion photoelectron spectra of deprotonated indole have been obtained utilizing several photon energies. The slow electron velocity-map imaging spectrum of indolide allows for the determination of the electron affinity (EA) of indolyl, 2.4315 ± 0.0017 eV. The equilibrium geometry of indolide was shown to minimally distort upon photodetachment with only ring distortion vibrational modes of A' symmetry becoming significantly excited. Photoelectron spectra of indolide accessing the electronic ground state of indolyl displayed a photon energy dependence due to electron autodetachment. Combining the EA of indolyl with the previous work studying the dissociation energy of H-indolyl allows for a new independent measure of ΔHN-H ≤ 348.7 kcal/mol, which improves the previous measurement of the gas phase acidity. The anion photoelectron spectrum of deprotonated indoline consisted of a featureless broad band extending from ∼1.3 eV to 1.7 eV electron binding energy. The congested nature of the spectrum is likely due to the presence of multiple isomers of deprotonated indoline, including ring-opened structures.

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“…The photoelectron spectra for HBDI -is reproduced from a previous study using the same experimental method. 33 As detailed in previous work, 46 pvinyl-phenolate, VPh -, was produced from CA -that underwent collisional-induced dissociation to lose CO 2 in the ion guide. The anionic fragment was then mass-selected in the time-offlight mass spectrometer before being irradiated to perform photoelectron imaging.…”

Section: Methodology Experimentalmentioning

confidence: 99%

“…56,57 Further detail on the Dyson orbitals used to model the D 0 and D 1 direct detachment channels accessed experimentally can be found in previous work. 46 Finally, the PADs for the two direct detachment channels were calculated using the ezDyson program (version 3.2) developed by Krylov and co-workers.…”

Section: Computationalmentioning

confidence: 99%

Chromophores of chromophores: a bottom-up Hückel picture of the excited states of photoactive proteins

Anstöter

Dean

Verlet

2017

Phys. Chem. Chem. Phys.

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Citation for published item:enst¤ oterD gte F nd henD ghrlie F nd erletD tn F F @PHIUA 9ghromophores of hromophores X ottomEup r¤ ukel piture of the exited sttes of phototive proteinsF9D hysil hemistry hemil physisFD IW @RRAF ppF PWUUPEPWUUWF Further information on publisher's website: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Here, we present a reductionist approach to gain fundamental insight into the evolution of electronic structure as the chromophore increases in complexity from phenolate to that in GFP. Using frequency-and angle-resolved photoelectron spectroscopy, in combination with electronic structure theory, the onset of excited states that are responsible for the characteristic spectroscopic features in biochromophores are determined. A comprehensive, yet intuitive picture of the effect of phenolate functionalisation is developed based on simple Hückel theory. Specifically, the first two bright excited states can be constructed from a linear combination of molecular orbitals localised on the phenolate and para-substituent groups. This essential interaction is first observed for p-vinyl-phenolate. This bottom-up approach offers a readily accessible framework for the design of photoactive chromophores.

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Sensitivity of Photoelectron Angular Distributions to Molecular Conformations of Anions

Cited by 18 publications

References 53 publications

Photoelectron Imaging and Quantum Chemistry Study of Phenolate, Difluorophenolate, and Dimethoxyphenolate Anions

Photoelectron Imaging and Quantum Chemistry Study of Phenolate, Difluorophenolate, and Dimethoxyphenolate Anions

Anion photoelectron spectroscopy of deprotonated indole and indoline

Chromophores of chromophores: a bottom-up Hückel picture of the excited states of photoactive proteins

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