Control of Photoinduced Donor-to-Acceptor Transfer Yield with Polarized Light
Not provided.
Chemistry↗
Engineering topics
Jin, Ye
Publications and source records attributed to Jin, Ye.
Introductory lecture: when the density of the noninteracting reference system is not the density of the physical system in density functional theory
We develop expressions for electron density defined through the linear response for general density functional approximations, demonstrating results for orbital functionals and for many-body perturbation theory, and explore the connections to developments in DFT.
Jin, Ye↗
Revisiting the Hole Size in Double Helical DNA with Localized Orbital Scaling Corrections
The extent of electronic wave function delocalization for the charge carrier (electron or hole) in double helical DNA plays an important role in determining the DNA charge transfer mechanism and kinetics. The size of the charge carrier’s wave function delocalization is regulated by the solvation induced localization and the quantum delocalization among the π stacked base pairs at any instant of time. Using a newly developed localized orbital scaling correction (LOSC) density functional theory method, we accurately characterized the quantum delocalization of the hole wave function in double helical B-DNA. This approach can be used to diagnose the extent of delocalization in fluctuating DNA structures. Our studies indicate that the hole state tends to delocalize among 4 guanine–cytosine (GC) base pairs and among 3 adenine–thymine (AT) base pairs when these adjacent bases fluctuate into degeneracy. The relatively small delocalization in AT base pairs is caused by the weaker π–π interaction. This extent of delocalization has significant implications for assessing the role of coherent, incoherent, or flickering coherent carrier transport in DNA.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Supported Single Fe Atoms Prepared via Atomic Layer Deposition for Catalytic Reactions
In this work, we report a general strategy to synthesize Fe single-atom catalysts (SACs) on various substrates (e.g., multiwalled carbon nanotubes, SiO 2 , and TiO 2 ) with high Fe loading (>1.5 wt %) by atomic layer deposition (ALD) through optimization of ferrocene (Fe precursor) dose time. Fe/SiO 2 and Fe/TiO 2 SACs were used for CO oxidation reactions and catalytic degradation of a methylene blue (MB) solution, respectively. Compared with reported iron oxide catalysts, the efficiency of Fe/SiO 2 for CO oxidation was more than 2 orders of magnitude higher than the reported values. The photocatalysis experiment demonstrated that TiO 2 nanoparticles, deposited with two cycles of Fe ALD, showed the highest activity and had a more than 6-fold photocatalytic activity enhancement over pure TiO 2 for the degradation of MB. This universal method, optimized Fe ALD, expands the potential applications of Fe SACs on different substrates.
36 MATERIALS SCIENCE↗
Excitation Energies from the Single-Particle Green’s Function with the GW Approximation
Quasi-particle energies are vital to predicting molecular ionization energies and bulk band structures. The state-of-the-art method for quasi-particle energy calculations, particularly for bulk systems, is the GW approximation. For excited state calculations, one needs to go beyond the GW approximation. The Bethe–Salpeter equation (BSE) is the commonly used approach for bulk-system excited state calculations beyond the GW approximation, which is accurate but computationally cumbersome. In this Article, we create a new method to extract excitation energies directly from the quasi-particle energies based on the GW approximation. Starting from the (N – 1)-electron system, we are able to calculate molecular excitation energies with orbital energies at the GW level for HOMO excitations. Our calculations demonstrate that this method can accurately capture low-lying local excitations as well as charge transfer excitations in many molecular systems. This approach is shown to outperform the time-dependent density functional theory (TDDFT) and are comparable with higher level excited state calculations, including the equation-of-motion couple cluster (EOM-CC) theory and the BSE, but with less computational effort. This new approach provides an efficient alternative to the BSE method for accurate excited state calculations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Renormalized Singles Green’s Function for Quasi-Particle Calculations beyond the G 0 W 0 Approximation
Quasi-particle energies and band gaps in particular are critical for investigating novel materials. Commonly used density functional approximations (DFAs) systematically underestimate band gaps, and GW approximation is the established method of choice for good accuracy and reliability. However, G 0 W 0 has some undesired dependence on the DFA, while self-consistent GW (scGW) is expensive and not consistent in accuracy improvement. Here a simple and efficient G RS W 0 approach has been developed: a subspace diagonalization of the Hartree-Fock (HF) Hamiltonian with the DFA density matrix provides the new reference Green's function GRS that incorporates the effect of all single excitation contributions to the self-energy, thereby essentially eliminating the starting-point dependence. Calculations for molecules and large band gap solids demonstrate the significant improvement over G 0 W 0 and greatly reduced dependence on the initial DFA. GRS W0 approach also improve results for other bulks over G 0 W 0 but to a lesser extent, which could be due to the limitations in current implementation for bulks. The results demonstrate that to achieve good accuracy, it is not necessary to use hybrid DFA, which is expensive for bulks. Lastly, this work should be greatly significant in making GW a more robust approach.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Photoluminescence properties and efficient energy transfer of Ce3+/Eu2+ activated K2Ba7Si16O40 phosphors
Highlights: • K{sub 2}Ba{sub 7}Si{sub 16}O{sub 40}:Ce{sup 3+}/Eu{sup 2+} phosphors have been synthesized by a high temperature solid-state method with CO atmosphere. • The resonance-type energy transfer by dipole-dipole interaction from Ce{sup 3+} to Eu{sup 2+} in K{sub 2}Ba{sub 7}Si{sub 16}O{sub 40} is demonstrated. • The critical distance between Ce{sup 3+} and Eu{sup 2+} ions is calculated to be 25.06 Å. • The thermal activation energy of K{sub 2}Ba{sub 7}Si{sub 16}O{sub 40} is calculated to be 0.26 eV. - Abstract: Ce{sup 3+}/Eu{sup 2+} activated K{sub 2}Ba{sub 7}Si{sub 16}O{sub 40} phosphors have been synthesized via a high-temperature solid-state method with CO atmosphere. Under ultraviolet (UV) light pump, the photoluminescence (PL) spectra of K{sub 2}Ba{sub 7}Si{sub 16}O{sub 40}: Ce{sup 3+} is composed of a broadband from 300 nm to 500 nm ascribed to the spin-allowed 5d–4f transition of Ce{sup 3+} ions. The optimal concentration is 8% for Ce{sup 3+} single doped K{sub 2}Ba{sub 7}Si{sub 16}O{sub 40} due to the ernergy dispersion between Ce{sup 3+} ions and the critical distance between Ce{sup 3+} ions is 15.05 Å. K{sub 2}Ba{sub 7}Si{sub 16}O{sub 40}: Eu{sup 2+} emits a broad green emission peaking at 498 nm. The spectral overlap between the emission of Ce{sup 3+} and the excitation of Eu{sup 2+} suggests the resonance-type energy transfer from Ce{sup 3+} to Eu{sup 2+}, which is further demonstrated by the decay curves of K{sub 2}Ba{sub 7}Si{sub 16}O{sub 40}: 8 mol% Ce{sup 3+}, m Eu{sup 2+}. The critical distance between Ce{sup 3+} and Eu{sup 2+} ions is calculated to be 25.06 Å by Dexter’s theory. Furthermore, the energy transfer mechanism is dipole-dipole interaction. In addition, the thermal activation energy is calculated to be 0.26 eV. The CIE coordinates can be tuned from blue to green by increasing Eu{sup 2+} ions. All results suggest that K{sub 2}Ba{sub 7}Si{sub 16}O{sub 40}: Ce{sup 3+}, Eu{sup 2+} is potentially useful for near-UV pumped white LEDs.
36 MATERIALS SCIENCE↗
Excitation energies from particle-particle random phase approximation with accurate optimized effective potentials
The optimized effective potential (OEP) that gives accurate Kohn-Sham (KS) orbitals and orbital energies can be obtained from a given reference electron density. These OEP-KS orbitals and orbital energies are used here for calculating electronic excited states with the particle-particle random phase approximation (pp-RPA). Our calculations allow the examination of pp-RPA excitation energies with the exact KS density functional theory (DFT). Various input densities are investigated. Specifically, the excitation energies using the OEP with the electron densities from the coupled-cluster singles and doubles method display the lowest mean absolute error from the reference data for the low-lying excited states. This study probes into the theoretical limit of the pp-RPA excitation energies with the exact KS-DFT orbitals and orbital energies. We believe that higher-order correlation contributions beyond the pp-RPA bare Coulomb kernel are needed in order to achieve even higher accuracy in excitation energy calculations.
74 ATOMIC AND MOLECULAR PHYSICS↗
Generalized Optimized Effective Potential for Orbital Functionals and Self-Consistent Calculation of Random Phase Approximations
A new self-consistent procedure for calculating the total energy with an orbital-dependent density functional approximation (DFA), the generalized optimized effective potential (GOEP), is developed in the present work. The GOEP is a nonlocal Hermitian potential that delivers the sets of occupied and virtual orbitals and minimizes the total energy. The GOEP optimization leads to the same minimum as does the orbital optimization. The GOEP method is promising as an effective optimization approach for orbital-dependent functionals, as demonstrated for the self-consistent calculations of the random phase approximation (RPA) to the correlation functionals in the particle–hole (ph) and particle–particle (pp) channels. The results show that the accuracy in describing the weakly interacting van der Waals systems is significantly improved in the self-consistent calculations. In particular, the important single excitations contribution in non-self-consistent RPA calculations can be captured self-consistently through the GOEP optimization, leading to orbital renormalization, without using the single excitations in the energy functional.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Multireference Density Functional Theory with Generalized Auxiliary Systems for Ground and Excited States
To describe static correlation, we create a new approach to density functional theory (DFT), which uses a generalized auxiliary system that is of a different symmetry, such as particle number or spin, from that of the physical system. The total energy of the physical system consists of two parts: the energy of the auxiliary system, which is determined with a chosen density functional approximation (DFA), and the excitation energy from an approximate linear response theory that restores the symmetry to that of the physical system, thus rigorously leading to a multideterminant description of the physical system. The electron density of the physical system is different from that of the auxiliary system and is uniquely determined from the functional derivative of the total energy with respect to the external potential. Our energy functional is thus an implicit functional of the physical system density, but an explicit functional of the auxiliary system density. We demonstrate that the total energy minimum and stationary states, describing the ground and excited states of the physical system, can be obtained by a self-consistent optimization with respect to the explicit variable, the generalized Kohn–Sham noninteracting density matrix. We have developed the generalized optimized effective potential method for the self-consistent optimization. Among options of the auxiliary system and the associated linear response theory, reformulated versions of the particle–particle random phase approximation (pp-RPA) and the spin-flip time-dependent density functional theory (SF-TDDFT) are selected for illustration of principle. Numerical findings show that our multireference DFT successfully describes static correlation in bond dissociation and double bond rotation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗