An MO theory of the cubic field splitting of 3d5 6S ions in II-IV compounds of Td symmetry
Molecular orbital techniques used to find cubic field splitting 3a of certain ions in periodic group II-VI compounds of T sub d symmetry
HAMILTONIAN↗
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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Toward an Understanding of Linear Scaling Relations through Energy Decomposition Analysis
The discovery of linear scaling relations has fundamentally changed the field of heterogeneous catalysis. The scaling relations have been rationalized based on the d-band theory, specifically a separation of sp and d electron contributions to adsorption energies. Within the framework of energy decomposition analysis, a full understanding of such a separation would require one to further break down the adsorption energy into distinct energy components such as electrostatics, polarization, charge transfer, and van der Waals interactions, and to examine the sp and d contributions to each of them. As a step in this direction, we analyzed the interaction energy between CH x (x = 1–4) adsorbates and fcc(100) transition metal surfaces (M = Cu, Ag, Au, Rh, and Pt), with the surfaces represented both as slabs in plane-wave density functional theory (pw-DFT) calculations and as atomic clusters in atomic-orbital basis density functional theory (ao-DFT) calculations. Through an absolutely localized molecular orbital (ALMO) based energy decomposition analysis of the ao-DFT adsorption energy, each of the interaction energy components (electrostatics, polarization, van der Waals, and charge transfer) was found to follow its own scaling relations, with an intricate interplay among these energy components yielding the overall scaling relations for the total adsorption energies. Using the recently introduced ALMO-based polarization and charge-transfer analysis schemes, we further dissected polarization into metal surface and adsorbate contributions, and charge transfer into metal → adsorbate and adsorbate → metal contributions. The contributions from the sp and d electrons of the metal to these terms were further quantified, and the dominant role of the metal d electrons was reaffirmed. These results shed light on how CHx adsorbates interact with metal surfaces and further reveal the physical origin of the scaling relations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Localized orbitals for arbitrary molecular wave functions.
Localized orbitals defined for arbitrary wave functions for atoms and molecules with even or odd number of electrons, noting positive trihydrogen ion
Certain, P. R.↗
New type of molecular perturbation treatment.
Perturbation treatment for molecular configuration using product of atomic or molecular orbits as zero-order wave function
WAVE FUNCTION↗
Shuttle/Payload Contamination Evaluation /SPACE/ - A systems level contamination model
The Shuttle/Payload Contamination Evaluation (SPACE) computer program was designed to three dimensionally synthesize the dynamics of the induced on-orbit molecular contaminant environment of the Shuttle Orbiter and a number of Spacelab payload carrier configurations. SPACE has the capability to accept any instrument or spacecraft configuration for contamination evaluation through manipulation of program input data. It represents a significant advancement over previous analytical or modeling techniques in that it is the first integrated systems level model of its type to collectively consider geometry (emphasizing surface shadowing), any arbitrary contaminant source(s) and the contaminant transport mechanisms of: (1) direct source-to-surface; (2) return flux due to molecular collisions with the ambient atmosphere and other contaminant molecules; and (3) reflection/reemission from structural surfaces.
Jarossy, F. J.↗
On the functional dependence of transition-potential coupled cluster
Orbital relaxation of the core region is a primary source of error in the computation of core ionization and core excitation energies. Recently, Transition-Potential Coupled Cluster (TP-CC) methods have been used to explicitly treat orbital relaxation using non-variational molecular orbitals determined by reoccupation of orbitals optimized for a fractional core occupation. The amount of fractional occupation is governed by parameter λ, and recommended values for accurate TP-CCSD and XTP-CCSD computations of carbon, nitrogen, oxygen, and fluorine K edges were previously determined. Herein, we explore the performance of several density functionals for generating the fractionally occupied orbitals used in TP-CCSD. These functionals include HF, BP86, BH&HLYP, B3LYP, M06-2X, and ωB97m-V. The fractionally occupied orbitals computed across the various functionals were subsequently employed as the initial orbitals for our TP-CCSD calculations of organic K-edge x-ray absorption and photoelectron spectra. Regardless of the functional used to generate the fractionally occupied orbitals, the TP-CCSD calculations yield accurate and comparable core ionization energies, core excitation energies, and oscillator strengths.
Coupled-cluster methods↗
Electronic states of molecules. i - self- consistent field calculations of the ground, ionized, and excited states of n sub 2 and o sub 2.
Ionization, excitation and total energies of oxygen and nitrogen, using self-consistent field molecular orbital method
SELF-CONSISTENT FIELD /SCF/↗
Ab initio calculation of the e super 1 sigma sub g and a super 3 sigma sub g super plus states of the hydrogen molecule.
Molecular orbital calculation of potential function for excited state of hydrogen molecule
MOLECULAR ORBIT↗
Molecular shield - An orbiting low-density materials laboratory
Analysis of a molecular shield orbited at 200 km utilizes the kinetic theory of a drifting Maxwellian gas, applied to a hemispherical shell geometry containing internal sources. The molecular shield provides very low gas density conditions for materials experiments at low gravity, while the hemispherical geometry minimizes the internal surface/volume ratio. Deployment of the shield in orbit is described. Contributions to density by shield outgassing, by experiment outgassing, and by interaction with the orbiter are discussed separately. A jettisonable closure plate sealing the hemisphere minimizes any risk of experiment contamination during deployment.
Melfi, L. T., Jr.↗
One-Body Properties and Their Perturbative Accuracy with Aufbau Suppressed Coupled Cluster Theory
In this work we derived and implemented the calculation of the one-body reduced density matrix for Aufbau suppressed coupled cluster theory, from which excited state natural orbitals and one-body properties, like atomic populations and dipole moments, are obtained. We utilized the natural orbitals to refine the ASCC solution for simple valence and Rydberg systems, exploring the process of repeatedly solving the ASCC equations in successive natural orbital bases to achieve independence from the starting molecular orbitals. For dipole moments in small molecules where high-level comparison data is available, we find that the accuracy of ASCC essentially matches that of linear response and equation-of-motion coupled cluster as long as care is taken to preserve the response's perturbative completeness.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Modified Iterative Extended Hueckel. 1: Theory
Iterative Extended Huekel is modified by inclusion of explicit effective internuclear and electronic interactions. The one electron energies are shown to obey a variational principle because of the form of the effective electronic interactions. The modifications permit mimicking of aspects of valence bond theory with the additional feature that the energies associated with valence bond type structures are explicitly calculated. In turn, a hybrid molecular, orbital valence, bond scheme is introduced which incorporates variant total molecular electronic density distributions similar to the way that Iterative Extended Hueckel incorporates atoms.
Aronowitz, S.↗
Scalable Quantum Monte Carlo Method for Polariton Chemistry via Mixed Block Sparsity and Tensor Hypercontraction Method
We present a reduced-scaling auxiliary-field quantum Monte Carlo (AFQMC) framework designed for large molecular systems and ensembles, with or without coupling to optical cavities. Our approach leverages the natural block sparsity of the Cholesky decomposition (CD) of electron repulsion integrals in molecular ensembles and employs tensor hypercontraction (THC) to efficiently compress low-rank Cholesky blocks. By representing the Cholesky vectors in a mixed format, keeping high-rank blocks in block-sparse form and compressing low-rank blocks with THC, we reduce the scaling of exchange-energy evaluation from quartic to robust cubic in the number of molecular orbitals N, while lowering memory from cubic toward quadratic. Benchmark analyses on one-, two-, and three-dimensional molecular ensembles (up to ∼1,200 orbitals) show that (a) the number of nonzeros in Cholesky tensors grows linearly with system size across dimensions; (b) the average numerical rank increases sublinearly and does not saturate at these sizes; and (c) rank heterogeneity─some blocks nearly full rank and many low rank, naturally motivates the proposed mixed block sparsity and THC scheme for efficient calculation of exchange energy. In conclusion, we demonstrate that the mixed scheme yields cubic wall-time scaling with favorable prefactors and preserves AFQMC accuracy.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Atomic Orbital Energy Matching vs Overlap in Actinide-Ligand Dative Bonding
Prebonding conditions and dative bond formation in actinide(IV)hexachloride complexes with U, Np, and Pu are studied by density functional theory (DFT) calculations, focusing on the interplay of atomic orbital (AO) overlap and AO energy matching in the formation of molecular orbitals (MOs) and the subsequent identification of dative bonds. The extent of donation is tracked via population analysis, MO localization, and bond-order criteria. DFT Fock matrices are used to setup models in which varying numbers of valence AOs interact to form dative bonds. The results confirm, among other effects, a contribution to metal−ligand covalency from the actinide (An) 6p shell. Better matching of An(5f) and Cl(3p) energies occurs as the An(5f) level stabilizes with increasing An effective nuclear charge. A near-degeneracy occurs in the case of the α-spin orbitals of the Pu system, but it is inconsequential. Altogether, better AO energy matching for An(5f) and Cl(3p) along the series U, Np, Pu is counter-balanced by decreasing AO overlap and decreasing availability of 5f acceptor orbitals, leading to similar bond orders and extents of donation in the three systems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Strong field ionization and dissociation dynamics of vinyl bromide (C 2 H 3 Br) initiated by few-cycle pulses
Photoelectron-photoion (PEPICO) and photoion-photoion (PIPICO) coincidence measurements, coupled with a few-cycle intense laser field, were employed to investigate strong field ionization/dissociation dynamics of vinyl bromide (C₂H₃Br). The angular streaking technique was used to map the recoil-frame angle-dependent ionization rates to identify ionizing orbitals. Dissociative single ionization was mainly attributed to ionizing the lower lying molecular orbitals, suggesting that direct ionization dominates with few-cycle pulses. Three dissociative double ionization channels, both prompt and delayed fragmentation, were identified. Theoretical analysis using time-dependent configuration interaction with complex absorbing potential (TDCI-CAP) and high-level electronic structure methods was performed to elucidate the underlying ionization and dissociation mechanisms.
Olowolafe, Temitayo A. [Wayne State University, De↗
Molecular outgassing measurements for an element of the Shuttle thermal protection system
Molecular outgassing studies were conducted on a thermal-protection material recently developed for the Shuttle Orbiter. Molecular outgassing rates as low as 10 to the minus 11th g/sq cm/sec, condensation coefficients, and molecular desorption rates were measured in four separate experiments using cryogenically and thermoelectrically cooled quartz crystal microbalances. Although the initial outgassing rates are high, they decreased to values in the 10 to the minus 10th g/sq cm/sec range in a reasonable period of time. Outgassing rates do not increase after entry heating although the condensation coefficients at various microbalance collection-surface temperatures become somewhat larger.
Visentine, J. T.↗
Long-Range Resonant Charge Transport through Open-Shell Donor–Acceptor Macromolecules
A grand challenge in molecular electronics is the development of molecular materials that can facilitate efficient longrange charge transport. Research spanning more than two decades has been fueled by the prospects of creating a new generation of miniaturized electronic technologies based on molecules whose synthetic tunability offers tailored electronic properties and functions unattainable with conventional electronic materials. However, current design paradigms produce molecules that exhibit off-resonant transport under low bias, which limits the conductance of molecular materials to unsatisfactorily low levels several orders of magnitude below the conductance quantum 1 G 0 and often results in an exponential decay in conductance with length. Here, we demonstrate a chemically robust, air-stable, and highly tunable molecular wire platform comprised of open-shell donor−acceptor macromolecules that exhibit remarkably high conductance close to 1 G 0 over a length surpassing 20 nm under low bias, with no discernible decay with length. Single-molecule transport measurements and ab initio calculations show that the ultralong-range resonant transport arises from extended π-conjugation, a narrow bandgap, and diradical character, which synergistically enables excellent alignment of frontier molecular orbitals with the electrode Fermi energy. The implementation of this long-sought-after transport regime within molecular materials offers new opportunities for the integration of manifold properties within emerging nanoelectronic technologies.
36 MATERIALS SCIENCE↗
Lewis Acid‐Activated Charge Trapping in Dielectric Polymers for Superior High‐Temperature Electrostatic Energy Storage
Dielectric polymer capacitors are essential for electrostatic energy storage but suffer from charge transport-induced energy losses, particularly at elevated temperatures where thermally activated charge carriers exacerbate conduction. Conventional mitigation strategies rely on introducing heterogeneous interfaces to create charge traps, complicating scalable film fabrication. A homogeneous molecular trapping mechanism would circumvent these complexities, yet remains underexplored. Herein, a charge trapping strategy is devised by modifying the lowest occupied molecular orbitals of dielectric polymers through Lewis acid-base adduct formation. The use of tris(pentafluorophenyl)boron (BCF) as a Lewis acidic molecular additive introduces deeper charge traps in commercial polyetherimide (PEI) while retaining homogeneity. With only 0.5 wt.% loading, the PEI-BCF film exhibits greatly improved breakdown strength, achieving an ultrahigh discharged energy density of 7.3 J cm-3 with excellent cycle stability at 200 °C. This work establishes a facile molecular approach to decoupling charge trapping from heterogeneous interfaces, enabling high-energy-density polymer capacitors operable under extreme thermal conditions.
Fan, Lu↗
Structure−Property Relationships in a Series of Hybrid Halopyridinium Ruthenium(IV) Halides
Reported is the synthesis and characterization of a family of hybrid ruthenium halides consisting of haloruthenium octahedra (X = Cl, Br) charge balanced with halopyridinium (XPy; X= H, Cl, Br, I) organic cations which assemble via noncovalent interactions between ion pairs. Diffuse reflectance spectroscopy showed that compounds containing RuBr 6 2- octahedra displayed a lower bandgap (1.05 eV< x < 1.08 eV) compared to compounds with RuCl 6 2- octahedra (1.22 eV < x < 1.43 eV). Additionally, computational density functional theory (DFT) based natural bonding orbital (NBO) analysis and density of state (DOS) methods were used to characterize second-sphere non-covalent interaction strengths and elucidate molecular orbital perturbations to elucidate their influence on Ru-X orbital constructs and in turn rationalize band gap trends. Analyses showed ligand to metal charge transfer is responsible for the small bandgap energies and are unperturbed by second-sphere interactions. Here, this report serves as a platform for probing the relationship between the structural and photophysical properties within the haloruthenium family of low dimensional transition metal halide perovskites.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗