Computational investigation of the photoinduced homolytic dissociation of water in the pyridine–water complex

Liu, Xiaojun; Sobolewski, Andrzej L.; Borrelli, Raffaele; Domcke, Wolfgang

doi:10.1039/c3cp44585b

Cited by 59 publications

(111 citation statements)

References 43 publications

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“…Excitation energies of the analogous triplet states were also computed using CASSCF, CASPT2 and ADC (2). As expected, these lie lower in energy than the singlet states involving the same orbital promotions (see fig.…”

Section: Physical Chemistry Chemical Physics Accepted Manuscriptmentioning

confidence: 70%

“…[38][39][40][41] Formation of the 1 ππ* state involves a LUMO ← HOMO electron promotion ( fig. ADC (2) predicts 4.60 eV.. The participating orbitals show good spatial overlap, which is reflected in a significant oscillator strength of this transition (table 2).…”

Section: (B) Hydroquinone (Bqh 2 )mentioning

confidence: 83%

“…It should be noted that BQ acts as a photobase in reaction (1), while BQH· acts as a photoacid in reaction (2). One key difference in the triplet states compared to the singlet states is the relative energy of the locally excited 3 ππ* state in the FC region compared to that of the 3 ππ*(CT) state, see figs.…”

Section: Excited-state Reactivity In the Bq-h 2 O Complex: Electron-dmentioning

confidence: 99%

“…The UV mediated photosynthesis of H 2 O and CO 2 [2][3][4] BQ is a photoactive chromophore that exhibits a large redox potential. It is therefore widely used as a hydrogen-accepting reagent in organic syntheses and serves as a dehydration agent.…”

Section: Introductionmentioning

confidence: 99%

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Photoinduced water splitting via benzoquinone and semiquinone sensitisation

Karsili

Tuna

Ehrmaier

et al. 2015

Phys. Chem. Chem. Phys.

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The splitting of water into H· and OH· radicals by sensitisation of a redox-active chromophore with sunlight may eventually become a viable way of producing unlimited, clean and sustainable energy. In this work, we explore the possibility of photo-oxidation of water via sensitisation of benzoquinone with ultraviolet (UV) light in the hydrogen-bonded complex of benzoquinone with a single water molecule. Using state-of-the-art quantum chemical calculations, the mechanisms of electron/proton transfer reactions between photoexcited benzoquinone and water are characterised. In the benzoquinone-H 2 O complex, photoexcitation of the chromophore leads to the population of locally excited ππ* and nπ* singlet states, which are coupled to hitherto unknown charge-transfer states. In the latter, an electron is transferred from the oxygen atom of the water molecule to the lowest π* orbital of benzoquinone. These charge-separated states drive the transfer of a proton from the water molecule to the carbonyl acceptor site, yielding the semiquinone-OH· biradical. Upon absorption of a second UV photon, the semiquinone radical may undergo O-H bond fission, which generates an H· radical and restores the benzoquinone photocatalyst. Our computational results shed light on long-standing questions regarding the nature of the photoreactive electronic states in the aqueous photochemistry of benzoquinone.

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Section: Physical Chemistry Chemical Physics Accepted Manuscriptmentioning

confidence: 70%

Section: (B) Hydroquinone (Bqh 2 )mentioning

confidence: 83%

Section: Excited-state Reactivity In the Bq-h 2 O Complex: Electron-dmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Photoinduced water splitting via benzoquinone and semiquinone sensitisation

Karsili

Tuna

Ehrmaier

et al. 2015

Phys. Chem. Chem. Phys.

Self Cite

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show abstract

“…While the second-order algebraic-diagrammatic construction (ADC(2)) method which is a singlereference Green's function method [31] and has been proved to be reliable in the calculation of the energy crossing [32,33] was used to optimize the geometries of the CT states as well as to calculate the vertical excitation energies and the potential energies of the CT states.…”

Section: Methodsmentioning

confidence: 99%

Intermolecular-charge-transfer-induced fluorescence quenching in protic solvent

Lin

Liu

Lou

et al. 2016

Journal of Molecular Structure

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The Role of Computational Chemistry in Discovering and Understanding Organic Photocatalysts for Renewable Fuel Synthesis

Prentice

Zwijnenburg

2021

Advanced Energy Materials

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In this review the role computational chemistry plays in helping to rationalize the ability of organic materials, such as conjugated polymers, to drive photocatalytic water splitting and CO2 reduction, and the discovery of new organic photocatalysts, is reviewed. The ways in which organic photocatalysts differ from their inorganic counterparts, the mechanism by which such materials, when illuminated, reduce protons or CO2 and oxidize water or sacrificial donors, and how this can be studied using computational methods, as well as the high‐throughput virtual screening of organic materials as photocatalysts, are discussed. Finally, the current opportunities and challenges associated with studying photocatalysts computationally, are examined.

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Computational investigation of the photoinduced homolytic dissociation of water in the pyridine–water complex

Cited by 59 publications

References 43 publications

Photoinduced water splitting via benzoquinone and semiquinone sensitisation

Photoinduced water splitting via benzoquinone and semiquinone sensitisation

Intermolecular-charge-transfer-induced fluorescence quenching in protic solvent

The Role of Computational Chemistry in Discovering and Understanding Organic Photocatalysts for Renewable Fuel Synthesis

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