Ueber die Isomerie der Formylphenylessigester

Wislicenus, Wilhelm

doi:10.1002/jlac.18962910108

Cited by 89 publications

(12 citation statements)

References 15 publications

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“…Chemical properties, including nuclear conformation, spectroscopy, and chemical reactivity, can often be dramatically modified by interaction with the surrounding medium (e.g., through solvation). − These environmental interactions could be steric , or specific electronic perturbations such as hydrogen bonding, dipole–dipole, or noncovalent interactions. − Unfortunately, treating the system and its surrounding environment with high levels of theory is computationally intractable.…”

Section: Theory Of Real-time Time-dependent Electronic Structure Methodsmentioning

confidence: 99%

Real-Time Time-Dependent Electronic Structure Theory

et al. 2020

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Real-time electronic structure methods provide an unprecedented view of electron dynamics and ultrafast spectroscopy on the atto-and femtosecond time scale with vast potential to yield new insights into the electronic behavior of molecules and materials. In this Review, we discuss the fundamental theory underlying various real-time electronic structure methods as well as advantages and disadvantages of each. We give an overview of the numerical techniques that are widely used for real-time propagation of the quantum electron dynamics with an emphasis on Gaussian basis set methods. We also showcase many of the chemical applications and scientific advances made by using real-time electronic structure calculations and provide an outlook of possible new directions. CONTENTS 1. Introduction 9951 2. Theory of Real-Time Time-Dependent Electronic Structure Methods 9953 2.1. Real-Time Time-Dependent Hartree−Fock and Density Functional Theory 9953 2.1.1. The Adiabatic Approximation in TDDFT 9955 2.1.2. Accuracy of TDHF and TDDFT 9956 2.2. Real-Time Time-Dependent Semi-Empirical Methods 9957 2.3. Real-Time Time-Dependent Configuration-Interaction Methods 9957 2.4. Real-Time Time-Dependent Coupled-Cluster Methods 9958 2.5. Real-Time Time-Dependent Two-Component and Relativistic Methods 9961 2.6. Real-Time Methods in Complex and Nonequilibrium Environments 9962 3. Numerical Techniques 9963 3.1. Basis Set Representations 9963 3.2. Time Propagation Methods 9963 3.3. Signal Processing 9964 4. Application of Real-Time Time-Dependent Electronic Structure Methods 9966 4.1. UV/Vis Spectroscopy 9966 4.2. X-ray Absorption Spectroscopy 9967 4.3. Excited State Absorption and Emission 9967 4.4. Charge Transfer, Plasmon Excitations, and Exciton Dynamics 9968 4.5. Nonlinear Properties and Multidimensional Spectroscopy 9971 4.6. Spin and Magnetization Dynamics 4.7. Electronic Circular Dichroism and Magnetic Circular Dichroism 4.8. Electron Dynamics in Strong Fields 5. Outlook

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Section: Theory Of Real-time Time-dependent Electronic Structure Methodsmentioning

confidence: 99%

Real-Time Time-Dependent Electronic Structure Theory

et al. 2020

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“…The ubiquitous nature of solvents and their pervasive usage in the chemical industry makes the study of solvent effects an important area of investigation. The fact that the presence and nature of solvents can affect chemical equilibria was recognized as early as 1896 with the concurrent revelation of the keto-enol tautomerism in 1,3-dicarbonyl compounds and the nitro-isonitro tautomerism of primary and secondary nitro compounds. − As evidenced by the seminal work of Menschutkin, it was also demonstrated early on that the rate of chemical reactions can be attuned through the prudent choice of solvents. The role of solvents in homogeneous catalysis has long been systematically investigated and appropriated for industrial applications for several hydrogen addition and abstraction processes, , oxosynthesis, − cross-coupling reactions, − cycloadditions, , etc.…”

Section: Introductionmentioning

confidence: 99%

Computational Investigation of Aqueous Phase Effects on the Dehydrogenation and Dehydroxylation of Polyols over Pt(111)

et al. 2019

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Prediction of solvation effects on the kinetics of elementary reactions occurring at metal−water interfaces is of high importance for the rational design of catalysts for the biomass and electrocatalysis communities. A lack of knowledge of the reliability of various computational solvation schemes for processes on metal surfaces is currently a limiting factor. Using a multilevel quantum mechanical/molecular mechanical (QM/MM) description of the potential energy surface, we determined characteristic time and length scales for typical free-energy perturbation (FEP) calculations of bond cleavages in ethylene glycol, a sugar surrogate molecule, over Pt(111). Our approach is based on our explicit solvation model for metal surfaces and the repetition of FEP calculations to estimate confidence intervals. Results indicate that aqueous phase effects on the free energies of elementary processes can be determined with 95% confidence intervals from limited configuration space sampling and the fixed charge approximation used in the QM/MM-FEP methodology of smaller 0.1 eV. Next, we computed the initial O−H, C−H, and C− OH bond cleavages in ethylene glycol over Pt(111) in liquid water utilizing two different metal−water interaction potentials. Our calculations predict that aqueous phase effects are small (<0.1 eV) for the C−H bond cleavage and the activation barrier of the C−OH bond cleavage. In contrast, solvation effects are large (>0.35 eV) for the O−H bond cleavage and the reaction free energy of the C−OH bond scission. While the choice of a different Pt−water force field can lead to differences in predicted solvation effects of up to 0.2 eV, the differences are usually smaller (<0.1 eV), and the trends are always the same. In contrast, implicit solvation methods appear to currently not be able to reliably describe solvation effects originating from hydrogen bonding for metal surfaces even qualitatively.

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“…Interactions between the system and the environment as they mutually evolve in time cause properties of the system to depend (in potentially nonobvious ways) on the environmental degrees of freedom. The environment can not only impose changes in the system’s conformation through steric interactions , but also significantly alter the system’s electronic structure via noncovalent interactions, leading to changes in the system’s response to electromagnetic fields − (i.e., spectroscopic properties) and chemical reactivity. − …”

mentioning

confidence: 99%

Coupling Real-Time Time-Dependent Density Functional Theory with Polarizable Force Field

Donati

Wildman

Caprasecca

et al. 2017

J. Phys. Chem. Lett.

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Real-time time-dependent density functional theory (RT-TDDFT) is a powerful tool for obtaining spectroscopic observables and understanding complex, time-dependent properties. Currently, performing RT-TDDFT calculations on large, fully quantum mechanical systems is not computationally feasible. Previously, polarizable mixed quantum mechanical and molecular mechanical (QM/MMPol) models have been successful in providing accurate, yet efficient, approximations to a fully quantum mechanical system. Here we develop a coupling scheme between induced dipole based QM/MMPol and RT-TDDFT. Our approach is validated by comparing calculated spectra with both real-time and linear-response TDDFT calculations. The model developed within provides an accurate method for performing RT-TDDFT calculations on extended systems while accounting for mutual polarization between the quantum mechanical and molecular mechanical regions.

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Ueber die Isomerie der Formylphenylessigester

Cited by 89 publications

References 15 publications

Real-Time Time-Dependent Electronic Structure Theory

Real-Time Time-Dependent Electronic Structure Theory

Computational Investigation of Aqueous Phase Effects on the Dehydrogenation and Dehydroxylation of Polyols over Pt(111)

Coupling Real-Time Time-Dependent Density Functional Theory with Polarizable Force Field

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