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Full potential energy curves, electronic configurations, spectroscopic parameters, dipole moments, and energetics of ground and excited electronic states of TaB and WB were studied using MRCI, MRCI+Q, CCSD(T), and DFT levels of theory.
The ability to predict the chemical and physical properties of a material is directly related to the structure and interactions of its electrons. For materials comprised of f-block elements (the lanthanides and actinides found in the last two rows of the periodic table), the complexity of electronic structure has presented great difficulty in understanding, modeling, and predicting material properties. The complexity of multiconfigurational ground state electronic structures is illustrated herein by the combinatorics of electron permutations within individual and cumulative occupancy configurations. A non-integer orbital occupancy representation of multiconfigurational ground states is described for superposition mixing between multiple near-energy degenerate occupancy configurations and generalized in such a way that established ground states are returned by approximation for elements with less-complex electronic structures. By considering the occupancy configurations as statistical mechanics macrostates, and the permutations of electrons as statistical mechanics microstates within those macrostates, an over-approximation of entropy for multiconfigurational elemental ground state electronic structures has been calculated.
Available electron collision cross section data concerning total and elastic scattering, vibrational excitation, and ionization for O2, CO, and CH4 have been critically reviewed, and a set of cross sections for modeling of planetary atmospheric behavior is recommended. Utilizing these recommended cross sections, we derived total electronic state excitation cross sections and upper limits for dissociation cross sections, which in the case of CH4 should very closely equal the actual dissociation cross section.
The electronic states of Zn2 are investigated by ab initio polarization configuration-interaction calculations. Molecular states dissociating to Zn(1S) + Zn(1S, 3P, 1P) and Zn(3P) + Zn(3P) are treated. Important effects from states arising from Zn(+)(25) + Zn(-)(2P) are found in the potential-energy curves and electronic-transition moments. A model calculation for Hg2 based on the Zn2 curves and including spin-orbit coupling leads to a new interpretation of the emission bands in Hg vapor.
Available electron collision cross section data concerning total and elastic scattering, vibrationalexcitation, and ionization for O_2, CO, and CH_4 have been critically reviewed, and a set of crosssections for modeling of planetary atmospheric behavior is recommended. Utilizing theserecommended cross sections, we derived total electronic state excitation cross sections and upperlimits for dissociation cross sections, which in the case of CH_4 should very closely equal the actualdissociation cross section.
Here, we present the open-source VOTCA-XTP software for the calculation of the excited-state electronic structure of molecules using many-body Green’s function theory in the GW approximation with the Bethe–Salpeter equation (BSE). This work provides a summary of the underlying theory and discusses the details of its implementation based on Gaussian orbitals, including resolution-of-identity techniques and different approaches to the frequency integration of the self-energy or acceleration by offloading compute-intensive matrix operations using graphics processing units in a hybrid OpenMP/Cuda scheme. A distinctive feature of VOTCA–XTP is the capability to couple the calculation of electronic excitations to a classical polarizable environment on an atomistic level in a coupled quantum- and molecular-mechanics (QM/MM) scheme, where a complex morphology can be imported from Molecular Dynamics simulations. The capabilities and limitations of the GW–BSE implementation are illustrated with two examples. First, we study the dependence of optically active electron–hole excitations in a series of diketopyrrolopyrrole-based oligomers on molecular-architecture modifications and the number of repeat units. Second, we use the GW–BSE/MM setup to investigate the effect of polarization on localized and intermolecular charge-transfer excited states in morphologies of low-donor content rubrene–fullerene mixtures. These showcases demonstrate that our implementation currently allows us to treat systems with up to 2500 basis functions on regular shared-memory workstations, providing accurate descriptions of quasiparticle and coupled electron–hole excited states of various characters on an equal footing.
A prominent goal in quantum chemistry is to solve the molecular electronic structure problem for ground state energy with high accuracy.
Excess charge on polar surfaces of ionic compounds is commonly described by the two-dimensional electron gas (2DEG) model, a homogeneous distribution of charge, spatially-confined in a few atomic layers. Here, by combining scanning probe microscopy with density functional theory calculations, we show that excess charge on the polar TaO 2 termination of KTaO 3 (001) forms more complex electronic states with different degrees of spatial and electronic localization: charge density waves (CDW) coexist with strongly-localized electron polarons and bipolarons. These surface electronic reconstructions, originating from the combined action of electron-lattice interaction and electronic correlation, are energetically more favorable than the 2DEG solution. They exhibit distinct spectroscopy signals and impact on the surface properties, as manifested by a local suppression of ferroelectric distortions.
Design criteria for solid state electronic, high speed iterative differential analyzer using integrated circuits
A new algorithm is presented for the numerical simulation of electrons in a quantum wire as described by a two-dimensional eigenvalue problem for Schroedinger's equation coupled with Poisson's equation. Initially, the algorithm employs an underrelaxed fixed point iteration to generate an approximation which is reasonably close to the solution. Subsequently, this approximate solution is employed as an initial guess for a Jacobian-free implementation of an approximate Newton method. In this manner the nonlinearity in the model is dealt with effectively. The effectiveness of this approach is demonstrated in a set of numerical experiments which study the electron states on the cross section of a quantum wire structure based on III-V semiconductors at 4.2 and 77 K.
We have carried out ab initio electronic structure calculations of the spin-orbit and rotation-orbit couplings among the 14 lowest electronic states of TiO and used them to predict ro-vibrational energy levels. We report on the qualitative results as well as our progress in optimizing our Hamiltonian parameters in order to improve agreement with experimental line positions,
We have carried out ab initio electronic structure calculations of the spin-orbit and rotation-orbit couplings among the 14 lowest electronic states of TiO and used them to predict ro-vibrational energy levels. We report on the qualitative results as well as our progress in optimizing our Hamiltonian parameters in order to improve agreement with experimental line positions.
Sodium hydride (NaH) in the gas phase presents a seemingly simple electronic structure making it a potentially tractable system for the detailed investigation of nonadiabatic molecular dynamics from both computational and experimental standpoints. The single vibrational degree of freedom, as well as the strong nonadiabatic coupling that arises from the excited electronic states taking on considerable ionic character, provides a realistic chemical system to test the accuracy of quasi-classical methods to model population dynamics where the results are directly comparable against quantum mechanical benchmarks. Here, using a simulated pump–probe type experiment, this work presents computational predictions of population transfer through the avoided crossings of NaH via symmetric quasi-classical Meyer–Miller (SQC/MM), Ehrenfest, and exact quantum dynamics on realistic, ab initio potential energy surfaces. The main driving force for population transfer arises from the ground vibrational level of the D 1 Σ + adiabatic state that is embedded in the manifold of near-dissociation C 1 Σ + vibrational states. When coupled through a sharply localized first-order derivative coupling most of the population transfers between t = 15 and t = 30 fs depending on the initially excited vibronic wavepacket. While quantum mechanical effects are expected due to the reduced mass of NaH, predictions of the population dynamics from both the SQC/MM and Ehrenfest models perform remarkably well against the quantum dynamics benchmark. Additionally, an analysis of the vibronic structure in the nonadiabatically coupled regime is presented using a variational eigensolver methodology.
Abstract Quantum coupling in arrayed nanostructures can produce novel mesoscale properties such as electronic minibands to improve the performance of optoelectronic devices, including ultra-efficient solar cells and infrared photodetectors. Colloidal PbSe quantum dots (QDs) that self-assemble into epitaxially-fused superlattices (epi-SLs) are predicted to exhibit such collective phenomena. Here, we show the emergence of distinct local electronic states induced by crystalline necks that connect individual PbSe QDs and modulate the bandgap energy across the epi-SL. Multi-probe scanning tunneling spectroscopy shows bandgap modulation from 0.7 eV in the QDs to 1.1 eV at their necks. Complementary monochromated electron energy-loss spectroscopy demonstrates bandgap modulation in spectral mapping, confirming the presence of these distinct energy states from necking. The results show the modification of the electronic structure of a precision-made nanoscale superlattice, which may be leveraged in new optoelectronic applications.
Partition functions for ground electronic states of positive simple H and trihydrogen molecular ions
Radiative mean lives and transition probabilities of electronic states in beam foil excited atomic and ionic carbon
Recent work on the development of single-reference perturbation theories for the study of excited electronic states will be discussed. The utility of these methods will be demonstrated by comparison to linear-response coupled-cluster excitation energies. Results for some halogen molecules of interest in stratospheric chemistry will be presented.
In this DOE Early Career project “Nanoscale Ferroelectric Control of Novel Electronic States in Layered Two-Dimensional Materials,” the PI’s group has combined ferroelectric field effect with nanoscale domain imaging and writing to design the electronic and optical properties of two-dimensional (2D) van der Waals materials, including graphene and transition metal dichalcogenides MoS2 and ReS2. The van der Waals materials have been prepared into field effect transistor (FET) devices with ferroelectric gates. Through domain patterning in a ferroelectric polymer PVDF-TrEF top-gate via conductive atomic force microscopy, the team has created programmable Schottky junctions in monolayer MoS 2 , where both barrier height and I-V rectifying polarity can be reconfigured. The transport anisotropy of monolayer to few-layer ReS 2 has been mapped out by defining the entire channel into an insulating state and creating nanoscale conducting paths along different directions through domain writing in the ferroelectric top-gate. The result shows that the conductivity along and perpendicular to the Re-chain can differ by >5.5x10 4 . Theoretical modeling points to the band origin of the transport anomaly and reveals the emergence of a flat band in few-layer ReS 2 . The interfacial epitaxial relation between ReS 2 and PVDF-TrFE further promotes the formation of close-packed, highly ordered PVDF-TrFE nanowires with width of 35 nm and 10 nm. Nonvolatile modulation of quantum Hall effect has been achieved in graphene FETs with a ferroelectric oxide Ba 0.4 Sr 0.6 TiO 3 back-gate. Scattering from the remote surface optical phonon in Ba 0.4 Sr 0.6 TiO 3 limits the room temperature mobility of graphene to be about 3x10 4 cm 2 /Vs. Steep-slope switching has been achieved in MoS 2 FETs back-gated by polycrystalline Pb(Zr,Ti)O 3 , which signals a static-state negative capacitance mode without involving an additional dielectric layer. Piezoresponse force microscopy studies show that the sub-threshold swing can be well correlated with the domain wall density in Pb(Zr,Ti)O 3 . The team also observes an unconventional filtering effect of the second harmonic generation response at the MoS 2 /Pb(Zr,Ti)O 3 heterointerface, which can be accounted for by the alignment between one of the polar axes of MoS 2 and the chiral dipole rotation at the surface of domain wall in Pb(Zr,Ti)O 3 . The research supported by this DOE grant has significantly advanced the fundamental understanding and functional design of ferroelectric/2D van der Waals heterostructures for their implementation towards energy applications.