Photoelectron spectroscopy of microsolvated benzophenone radical anions to reveal the origin of solvatochromic shifts in alcoholic media

Maeyama, Toshihiko; Yagi, Izumi; Fujii, Asuka; Mikami, Naohiko

doi:10.1016/j.cplett.2008.03.055

Cited by 8 publications

(26 citation statements)

References 17 publications

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“…Therefore, it is apparent that the first two MeOH molecules produce the approximately equal solvation energies. A similar size dependence in VDE shifts has been observed for the case of Bp – ·(MeOH) n . Revised data of photoelectron spectra of Bp – ·(MeOH) n are provided in the Supporting Information, which have improved the S/N ratio in comparison with the previous report.…”

Section: Results and Discussionsupporting

confidence: 79%

“…In our previous study on Bp – ·(MeOH) n , it was found that the photoabsorption peak energy for n = 5 considerably approaches the limit of the condensed phases. The rapid convergence of the absorption peak shifts relative to the VDE shifts is caused by the change of the local electron distribution occurring upon the photoabsorption, which is not effectively affected by interactions with the far-side solvent molecules . Thus, we expect that it is also true for the case of Fl – ·(MeOH) n .…”

Section: Results and Discussionmentioning

confidence: 89%

“…Experimental procedures in this work are similar to those described elsewhere. − Cluster anions of Fl – were generated with slow electron attachment in a supersonic expansion of a mixture of sample vapor seeded in argon gas at 2 atm. The vapor pressure of fluorenone in a sample container was enhanced with heating up to 110 °C, whereas methanol was vaporized in a separate container at room temperature.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

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Photodetachment Spectroscopy of Fluorenone Radical Anions Microsolvated with Methanol: Rationalizing the Anomalous Solvatochromic Behavior Due to Hydrogen Bonding

et al. 2015

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The attribution of the extraordinary blue shift for the intramolecular charge-transfer absorption band of fluorenone radical anion solvated in protic media was investigated by means of photodetachment spectroscopy of the gas-phase anions microsolvated with methanol, in conjunction with quantum chemical calculations based on density functional theory. Sequential shifts of the vertical detachment energy as a function of the cluster size are consistent with theoretical predictions, where up to two methanol molecules can directly attach to the carbonyl group. In the photodetachment excitation spectra as alternatives to the photoabsorption spectra, with increasing cluster size, a new absorption band grows in the higher-energy region, which coincides with the blue-shifted band in protic media. Spectral simulations using time-dependent density functional theory with the CAM-B3LYP functional reproduced the feature of the phenomenon. Analyses on the electronic configuration elucidated that the extraordinarily blue shifts originate from energy-level repulsion due to solvation-induced resonant coupling with another electronic state. The orbital transition for the counterpart state corresponds to the first absorption band of the neutral fluorenone molecule, which has small oscillator strength from the ground state. It was found that correction of long-range electron exchange correlation is important for the spectral simulation involving the electronic-state coupling.

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Section: Results and Discussionsupporting

confidence: 79%

Section: Results and Discussionmentioning

confidence: 89%

Section: Experimental and Computational Methodsmentioning

confidence: 99%

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Photodetachment Spectroscopy of Fluorenone Radical Anions Microsolvated with Methanol: Rationalizing the Anomalous Solvatochromic Behavior Due to Hydrogen Bonding

et al. 2015

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“…Despite being closed-shell, these species are notorious as challenging cases for theoretical investigations. Molecules were divided into four test sets based on their structural features, excited-state properties, and real-life applications, including polycyclic aromatic hydrocarbons (PAH), − organic photovoltaic (OPV) materials, ,,,,,,− ...…”

Section: Theorymentioning

confidence: 99%

Triplet Tuning: A Novel Family of Non-Empirical Exchange–Correlation Functionals

Lin

Voorhis

2019

J. Chem. Theory Comput.

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In the framework of density functional theory (DFT), the lowest triplet excited state, T 1 , can be evaluated using multiple formulations, the most straightforward of which are unrestricted DFT (UDFT) and time-dependent DFT (TDDFT). Assuming the exact exchangecorrelation (XC) functional is applied, UDFT and TDDFT provide identical energies for T 1 (E T ), which is also a constraint that we require our XC functionals to obey. However, this condition is not satisfied by most of the popular XC functionals, leading to inaccurate predictions of low-lying, spectroscopically and photochemically important excited states, such as T 1 and the lowest singlet excited state (S 1 ). Inspired by the optimal tuning strategy for frontier orbital energies [T. Stein, L. Kronik, and R. Baer, J. Am. Chem. Soc. 131, 2818 (2009)], we proposed a novel and non-empirical prescription of constructing an XC functional in which the agreement between UDFT and TDDFT in E T is strictly enforced. Referred to as "triplet tuning", our procedure allows us to formulate the XC functional on a case-by-case basis using the molecular structure as the exclusive input, without fitting to any experimental data. The first triplet tuned XC functional, TT-ωPBEh, is formulated as a long-range-corrected (LRC) hybrid of Perdew-Burke-Ernzerhof (PBE) and Hartree-Fock (HF) functionals [M. A. Rohrdanz, K. M. Martins, and J. M. Herbert, J. Chem. Phys. 130, 054112 (2009)] and tested on four sets of large organic molecules. Compared to existing functionals, TT-ωPBEh manages to provide 1 arXiv:1806.00317v3 [physics.chem-ph] 15 Jan 2019more accurate predictions for key spectroscopic and photochemical observables, including but not limited to E T , the optical band gap (E S ), the singlet-triplet gap (∆E ST ), and the vertical ionization potential (I ⊥ ), as it adjusts the effective electron-hole interactions to arrive at the correct excitation energies. This promising triplet tuning scheme can be applied to a broad range of systems that were notorious in DFT for being extremely challenging.

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“…This benchmark set, probably, is a good option for testing the ST gaps, as it comprises molecules that have either diradical or diradicaloid electronic characteristic in their electronic ground states. The second set was adopted from a recent work of Van Voorhis, where various kinds of polycyclic aromatic hydrocarbons, − new organic PV materials, − and thermally activated delayed fluorescence emitters were studied. − The majority of the molecules in the set are large-sized organic molecules and are used or potentially can be used in various real-life applications. The calculations with the set of Zimmerman were performed with the B3LYP, PBE0, BHHLYP, and B(0.15)HF(0.85)-LYP density functionals.…”

Section: Computational Detailsmentioning

confidence: 99%

Performance Analysis and Optimization of Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory (MRSF-TDDFT) for Vertical Excitation Energies and Singlet–Triplet Energy Gaps

et al. 2019

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The mixed-reference spin-flip (MRSF) time-dependent density functional theory (TDDFT) method eliminates the notorious spin contamination of SF-TDDFT, thus enabling identification of states of proper spin-symmetry for automatic geometry optimization and molecular dynamics simulations. Here, we analyze and optimize the MRSF-TDDFT in the calculations of the vertical excitation energies (VEEs) and the singlet−triplet (ST) gaps. The dependence of the obtained VEEs and ST gaps on the intrinsic parameters of the MRSF-TDDFT method is investigated, and prescriptions for the proper use of the method are formulated. For VEEs, MRSF-TDDFT displays similar or better accuracy than SF-TDDFT (ca. 0.5 eV), while considerably outperforming the LR-TDDFT for the ST gaps. As a result, a new functional of STG1X (dubbed here), especially for ST gaps is suggested on the basis of splitting between the components of the atomic multiplets.

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Photoelectron spectroscopy of microsolvated benzophenone radical anions to reveal the origin of solvatochromic shifts in alcoholic media

Cited by 8 publications

References 17 publications

Photodetachment Spectroscopy of Fluorenone Radical Anions Microsolvated with Methanol: Rationalizing the Anomalous Solvatochromic Behavior Due to Hydrogen Bonding

Photodetachment Spectroscopy of Fluorenone Radical Anions Microsolvated with Methanol: Rationalizing the Anomalous Solvatochromic Behavior Due to Hydrogen Bonding

Triplet Tuning: A Novel Family of Non-Empirical Exchange–Correlation Functionals

Performance Analysis and Optimization of Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory (MRSF-TDDFT) for Vertical Excitation Energies and Singlet–Triplet Energy Gaps

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