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The Importance of Being Inconsistent
10.1146/annurev-physchem-052516-044957 2017-05-02 We review the role of self-consistency in density functional theory (DFT). We apply a recent analysis to both Kohn–Sham and orbital-free DFT, as well as to partition DFT, which generalizes all aspects of standard DFT. In each case, the analysis distinguishes ... |
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Extending Quantum Chemistry of Bound States to Electronic Resonances
10.1146/annurev-physchem-052516-050622 2017-05-02 Electronic resonances are metastable states with finite lifetime embedded in the ionization or detachment continuum. They are ubiquitous in chemistry, physics, and biology. Resonances play a central role in processes as diverse as DNA radiolysis, plasmonic ca... |
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Roaming: A Phase Space Perspective
10.1146/annurev-physchem-052516-050613 2017-05-02 In this review we discuss the recently described roaming mechanism for chemical reactions from the point of view of nonlinear dynamical systems in phase space. The recognition of the roaming phenomenon shows the need for further developments in our fundamenta... |
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Ultrafast X-Ray Crystallography and Liquidography
10.1146/annurev-physchem-052516-050851 2017-05-02 Time-resolved X-ray diffraction provides direct information on three-dimensional structures of reacting molecules and thus can be used to elucidate structural dynamics of chemical and biological reactions. In this review, we discuss time-resolved X-ray diffra... |
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The Hydrated Electron
10.1146/annurev-physchem-052516-050816 2017-05-02 Existence of a hydrated electron as a byproduct of water radiolysis was established more than 50 years ago, yet this species continues to attract significant attention due to its role in radiation chemistry, including DNA damage, and because questions persist... |
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Random-Phase Approximation Methods
10.1146/annurev-physchem-040215-112308 2017-05-02 Random-phase approximation (RPA) methods are rapidly emerging as cost-effective validation tools for semilocal density functional computations. We present the theoretical background of RPA in an intuitive rather than formal fashion, focusing on the physical p... |
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Calculating Natural Optical Activity of Molecules from First Principles
10.1146/annurev-physchem-052516-044827 2017-05-02 Computations of natural optical activity (OA) from first principles (ab initio) have become indispensable in chiroptical studies of molecular systems. Calculations are used to assign absolute configurations and to analyze chiroptical data, providing a basis f... |
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Hot Charge Carrier Transmission from Plasmonic Nanostructures
10.1146/annurev-physchem-052516-044948 2017-05-02 Surface plasmons have recently been harnessed to carry out processes such as photovoltaic current generation, redox photochemistry, photocatalysis, and photodetection, all of which are enabled by separating energetic (hot) electrons and holes—processes that, ... |
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Computational Analysis of Vibrational Sum Frequency Generation Spectroscopy
10.1146/annurev-physchem-052516-044806 2017-05-02 Vibrational sum frequency generation (VSFG) spectroscopy is a widely used probe of interfaces and, having ideal surface sensitivity and selectivity, is particularly powerful when applied to wet and soft interfaces. Although VSFG spectroscopy can sensitively d... |
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Ion–Molecule Reaction Dynamics
10.1146/annurev-physchem-052516-044918 2017-05-02 We review the recent advances in the investigation of the dynamics of ion–molecule reactions. During the past decade, the combination of single-collision experiments in crossed ion and neutral beams with the velocity map ion imaging detection technique has en... |