Exploring the Aqueous Vertical Ionization of Organic Molecules by Molecular Simulation and Liquid Microjet Photoelectron Spectroscopy

Tentscher, Peter R.; Seidel, Robert; Winter, Bernd; Guerard, Jennifer J.; Arey, J. Samuel

doi:10.1021/jp508053m

Cited by 40 publications

(69 citation statements)

References 101 publications

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“…The best estimates of < VEG > ∞ (EFP, Born) also agree well with the previous theoretical estimates by Tentscher et al [32]. The close values of VEGs for charged species (ionization of anions and attachment to cations) is likely due to a favorable error cancellation: the cluster sphere radius (Fig.…”

supporting

confidence: 90%

“…The sampling is usually performed for an infinite system or a system with proper boundary conditions, however, the VEGs are often computed for truncated systems, assuming their convergence with respect to the system size [16,23,31,32]. Although the size of such model clusters is quite large (30)(31)(32)(33)(34)(35) A), here we show that the respective VEGs still differ from the bulk values. In fact, the VEGs (as well as ∆ r G Ox and λ) computed using finite cluster models depend linearly on the inverse radius of the solvation sphere.…”

mentioning

confidence: 76%

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Free Energies of Redox Half-Reactions from First-Principles Calculations

Tazhigulov

Bravaya

2016

J. Phys. Chem. Lett.

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Quantitative prediction of the energetics of redox half-reactions is still a challenge for modern computational chemistry. Here, we propose a simple scheme for reliable calculations of vertical ionization and attachment energies, as well as of redox potentials of solvated molecules. The approach exploits linear response approximation in the context of explicit solvent simulations with spherical boundary conditions. It is shown that both vertical ionization energies and vertical electron affinities, and, consequently redox potentials, exhibit linear dependence on the inverse radius of the solvation sphere. The explanation of the linear dependence is provided, and an extrapolation scheme is suggested. The proposed approach accounts for the specific short-range interactions within hybrid DFT and effective fragment potential approach as well as for the asymptotic system-size effects. The computed vertical ionization energies and redox potentials are in excellent agreement with the experimental values.

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confidence: 90%

mentioning

confidence: 76%

Free Energies of Redox Half-Reactions from First-Principles Calculations

Tazhigulov

Bravaya

2016

J. Phys. Chem. Lett.

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“…Given that a QM treatment of solvent might be desirable, the careful researcher may next wonder how much solvent should be treated quantum mechanically. A number of studies have explored this question for different molecular properties, [61][62][63][64][65][66] and the study of convergence of excitation energies with increasing size of molecular environment has become an area of active research. [10][11][12][67][68][69] Although in some systems a large amount of QM solvent may not be critical for accurately computing the property of interest, we have found that for excited states, values within approximately 0.05 eV of the converged value can be obtained with a full solvation shell treated with QM, as shown in Figure 3.…”

Section: Combining Qm Explicit Solvent With Classical Solvent Modelsmentioning

confidence: 99%

Modeling absorption spectra of molecules in solution

Zuehlsdorff

Isborn

2018

Int J of Quantum Chemistry

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The presence of solvent tunes many properties of a molecule, such as its ground and excited state geometry, dipole moment, excitation energy, and absorption spectrum. Because the energy of the system will vary depending on the solvent configuration, explicit solute-solvent interactions are key to understanding solution-phase reactivity and spectroscopy, simulating accurate inhomogeneous broadening, and predicting absorption spectra. In this tutorial review, we give an overview of factors to consider when modeling excited states of molecules interacting with explicit solvent. We provide practical guidelines for sampling solute-solvent configurations, choosing a solvent model, performing the excited state electronic structure calculations, and computing spectral lineshapes. We also present our recent results combining the vertical excitation energies computed from an ensemble of solute-solvent configurations with the vibronic spectra obtained from a small number of frozen solvent configurations, resulting in improved simulation of absorption spectra for molecules in solution.excited states, TDDFT, solvation, inhomogeneous broadening, absorption spectra | INTRODUCTIONThe presence of solvent around a molecule affects its energy, properties, dynamics, and reactivity, in both the ground and excited state. Because many excited state phenomena of chemical interest happen in solution and in complex interfacial environments, including photosynthesis, photocatalysis, photoinduced charge and proton transfer, and fluorescence in biological systems, it is important to be able to model these excited state reactions while accurately simulating the solvent environment. In addition, both static and time-resolved absorption and fluorescence spectroscopies serve as useful tools to elucidate chemical reactions and pathways, and simulation of these solution-phase spectra can help to achieve understanding of the electronic rearrangements governing chemical reactions.If theoretical models are to provide reliable simulations of solution-phase chemistry, accurate models of the solvent environment are required.The solvent environment can have a strong influence on an absorption spectrum due to polarization and direct solute-solvent interactions such as hydrogen bonding. Therefore, the modeling of absorption spectra of molecules in solution is often considered a vital step in developing and benchmarking methods to account for the complex solvent environment.Although continuum solvent approaches are computationally attractive because they use the bulk properties of the solvent to polarize a solute, and thus, usually do not sample solute-solvent configurations, in reality it is specific solvent configurations rather than a solvent continuum that determine excited state properties. Also, the simulation of spectral lineshapes, such as those shown in Figure 1 that include both the highenergy tail due to vibronic transitions and the inhomogeneous broadening due to solute-solvent interactions, poses a significant challenge for continuum methods. T...

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“…While photoelectron spectra for aqueous solutions were reported already in 1980s, [1] reliable data were not available until the development of a liquid micro jet technique. [2][3][4] With this approach, the electronic structure of water [5] and various hydrated solutes was characterized, including nucleic acid components and its analogues, [6][7][8][9] amino acids and other biomolecules, [10] organic molecules, [11][12][13] anions, [14,15] or various coordination compounds. [16][17][18] The PES technique is furthermore surface sensitive which allows for characterization of the liquid surfaces.…”

Section: Introductionmentioning

confidence: 99%

Efficient modeling of liquid phase photoemission spectra and reorganization energies: Difficult case of multiply charged anions

2017

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An efficient approach for quantitative modeling of liquid phase photoelectron spectra, reorganization energies, and redox potentials with DFT-based molecular dynamics simulations is presented. The method is based on a large scale cluster-continuum approach combined with the so-called reflection principle (RP). Finite size clusters of solute molecules with solvating water molecules are at first generated using either classical molecular dynamics or molecular dynamics with a quantum thermostat which accounts for nuclear quantum effects. In the next step, the electron binding energies are calculated. Finite-size corrections for (i) positions of electron binding energies and (ii) width of the spectrum are evaluated via a dielectric continuum approach. The performance of such a reflection principle with additional broadening approach (RP-AB) for oxidation of multiply charged iron anions, [Fe(CN) ] and [Fe(CN) ] is demonstrated. The role of nuclear quantum effects is discussed as well as the relation between spectroscopic data and electrochemical quantities. Results are compared with recent liquid photoemission experiments, explaining the obstacles for applying liquid phase photoemission spectroscopy as a direct method for obtaining absolute redox potentials and suggesting a way to overcome them. © 2017 Wiley Periodicals, Inc.

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Exploring the Aqueous Vertical Ionization of Organic Molecules by Molecular Simulation and Liquid Microjet Photoelectron Spectroscopy

Cited by 40 publications

References 101 publications

Free Energies of Redox Half-Reactions from First-Principles Calculations

Free Energies of Redox Half-Reactions from First-Principles Calculations

Modeling absorption spectra of molecules in solution

Efficient modeling of liquid phase photoemission spectra and reorganization energies: Difficult case of multiply charged anions

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