First-Principle Protocol for Calculating Ionization Energies and Redox Potentials of Solvated Molecules and Ions: Theory and Application to Aqueous Phenol and Phenolate

Ghosh, Debashree; Roy, Anirban; Seidel, Robert; Winter, Bernd; Bradforth, Stephen E.; Krylov, Anna I.

doi:10.1021/jp301925k

Cited by 135 publications

(297 citation statements)

References 111 publications

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“…This effect is accounted for by computing additive energy corrections to the excitation energies [310]. The combination of first-prinicple polarisable explict solvents with the EOM-CC family of methods is a unique feature of Q-CHEM, enabling state-of-the art calculations of solvatochromic effects and redox processes [312,313]. To sum up, the major differences between the QM/EFP and QM/MM schemes are: (1) more accurate and detailed description of the electrostatic interactions in EFP using distributed multipoles up to octopoles versus the partial charge representation used in typical MM; (2) polarisable environment in EFP induces self-consistent response to the electronic wave function of the quantum region, while most classical force fields are not polarisable.…”

Section: Qm/mm and Fragment Methodsmentioning

confidence: 99%

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Shao¹,

Gan²,

Epifanovsky³

et al. 2014

Molecular Physics

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A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and openshell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller-Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly correlated Cr 2 dimer, exploring zeolitecatalysed ethane dehydrogenation, energy decomposition analysis of a charged ter-molecular complex arising from glycerol photoionisation, and natural transition orbitals for a Frenkel exciton state in a nine-unit model of a self-assembling nanotube.Keywords quantum chemistry, software, electronic structure theory, density functional theory, electron correlation, computational modelling, Q-Chem Disciplines Chemistry CommentsThis article is from Molecular Physics: An International Journal at the Interface Between Chemistry and Physics 113 (2015): 184, doi:10.1080/00268976.2014. RightsWorks produced by employees of the U.S. Government as part of their official duties are not copyrighted within the U.S. The content of this document is not copyrighted. Authors 185A summary of the technical advances that are incorporated in the fourth major release of the Q-CHEM quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller-Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly corre...

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Section: Qm/mm and Fragment Methodsmentioning

confidence: 99%

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Shao¹,

Gan²,

Epifanovsky³

et al. 2014

Molecular Physics

Self Cite

2,748

2,077

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“…First, the fact that p-MePhSH in ethanol has a lower VIP (7.2 eV) 41 than PhOH in water (7.9 eV) 30 shows that a lower VIP does not necessarily predicate a larger autoionization yield.…”

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Exploring Autoionization and Photoinduced Proton-Coupled Electron Transfer Pathways of Phenol in Aqueous Solution

Oliver

Zhang

Roy

et al. 2015

J. Phys. Chem. Lett.

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The excited state dynamics of phenol in water have been investigated using transient absorption spectroscopy. Solvated electrons and vibrationally cold phenoxyl radicals are observed upon 200 nm and 267 nm excitation, but with formation timescales that differ by more than four orders of magnitude. The impact of these findings is assessed in terms of the relative importance of autoionization versus proton-coupled electron transfer mechanisms in this computationally tractable model system. TOC GRAPHIC

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“…Experimentally, recent developments in liquid microjet techniques 15,16 enabled the measurement of photoelectrons emitted directly from the liquid solutions and constituted a fundamental step forward in understanding the electronic properties of aqueous solutions. From a theoretical standpoint, only few interpretations or predictions 15,[17][18][19][20] of photoelectron spectra appeared in the literature; indeed, the microscopic description of aqueous solutions from first principles remains a challenging task, both from a theoretical and computational standpoint, and especially so in the case of anions, whose electronic structure is in general more complex than that of cations. 7,21,22 In this paper, we consider a chloride anion in aqueous solution and report an analysis of its electronic properties based on first principles molecular dynamics (MD) using several levels of theory; these include semi-local (Perdew-BurkeErnzerhof (PBE) 23,24 ) and hybrid (PBE0 25 ) functionals and many body perturbation theory (MBPT) 26 within the G 0 W 0 approximation.…”

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confidence: 99%

Communication: Electronic structure of the solvated chloride anion from first principles molecular dynamics

Zhang

Pham

Gygi

et al. 2013

The Journal of Chemical Physics

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We present first principles molecular dynamics simulations of the chloride anion in liquid water performed using gradient-corrected and hybrid density functionals. We show that it is necessary to use hybrid functionals both for the generation of molecular dynamics trajectories and for the calculation of electronic states in order to obtain a qualitatively correct description of the electronic properties of the solution. In particular, it is only with hybrid functionals that the highest occupied molecular orbital of the anion is found above the valence band maximum of water, consistent with photoelectron detachment measurements. Similar results were obtained using many body perturbation theory within the G0W0 approximation.

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First-Principle Protocol for Calculating Ionization Energies and Redox Potentials of Solvated Molecules and Ions: Theory and Application to Aqueous Phenol and Phenolate

Cited by 135 publications

References 111 publications

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Exploring Autoionization and Photoinduced Proton-Coupled Electron Transfer Pathways of Phenol in Aqueous Solution

Communication: Electronic structure of the solvated chloride anion from first principles molecular dynamics

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