A QM/MM equation-of-motion coupled-cluster approach for predicting semiconductor color-center structure and emission frequencies

Valence excitation spectra are computed for all deep-center silicon-vacancy defect types in 3C, 4H, and 6H silicon carbide (SiC) and comparisons are made with literature photoluminescence measurements. Nuclear geometries surrounding the defect centers are optimized within a Gaussian basis-set framework using many-body perturbation theory or density functional theory (DFT) methods, with computational expenses minimized by a QM/MM technique called SIMOMM. Vertical excitation energies are subsequently obtained by applying excitation-energy, electron-attached, and ionized equation-of-motion coupled-cluster (EOMCC) methods, where appropriate, as well as time-dependent (TD) DFT, to small models including only a few atoms adjacent to the defect center. We consider the relative quality of various EOMCC and TD-DFT methods for (i) energy-ordering potential ground states differing incrementally in charge and multiplicity, (ii) accurately reproducing experimentally measured photoluminescence peaks, and (iii) energy-ordering defects of different types occurring within a given polytype. The extensibility of this approach to transition-metal defects is also tested by applying it to silicon-substitutional chromium defects in SiC and comparing with measurements. It is demonstrated that, when used in conjunction with SIMOMM-optimized geometries, EOMCC-based methods can provide a reliable prediction of the ground-state charge and multiplicity, while also giving a quantitative description of the photoluminescence spectra, accurate to within 0.1 eV of measurement in all cases considered.Comment: 13 pages, 4 figures, 6 tables, 5 equations, 100 reference

The Lowest-Energy Isomer of C2Si2H4 Is a Bridged Ring: Reinterpretation of the Spectroscopic Data Based on DFT and Coupled-Cluster Calculations

The lowest-energy isomer of C2Si2H4 is determined by high-accuracy ab initio calculations to be the bridged four-membered ring 1,2-didehydro-1,3-disilabicyclo[1.1.0]butane (1), contrary to prior theoretical and experimental studies favoring the three-member ring silylsilacyclopropenylidene (2). These and eight other low-lying minima on the potential energy surface are characterized and ordered by energy using the CCSD(T) method with complete basis set extrapolation, and the resulting benchmark-quality set of relative isomer energies is used to evaluate the performance of several comparatively inexpensive approaches based on many-body perturbation theory and density functional theory (DFT). Double-hybrid DFT methods are found to provide an exceptional balance of accuracy and efficiency for energy-ordering isomers. Free energy profiles are developed to reason the relatively large abundance of isomer 2 observed in previous measurements. Infrared spectra and photolysis reaction mechanisms are modeled for isomers 1 and 2, providing additional insight about previously reported spectra and photoisomerization channels

TOWARDS A MECHANISM FOR FORMATION OF SILICON CARBIDE CRYSTALS IN AGB STARS

Silicon carbide (SiC) grains comprise a significant fraction of the dust found around carbon-rich AGB stars. Their presence in the interstellar medium is thought to originate from self-assembly of organosilicon building blocks, including previously observed species such as carborundum and cyclic silicon dicarbide ({\it c}-SiC$_2$). However, the actual formation mechanisms of even these simple silicon-bearing organic molecules remains elusive. Here it is proposed that disilyne (Si$_2$H$_2$) reacts barrierlessly with abundant acetylene (C$_2$H$_2$) on a spin-conserving potential to form C$_2$Si$_2$H$_4$. This species has been shown in experimental and theoretical studies\footnote{Lutz J.J., Inorganics, {\it submitted}} to photoisomerize under UV irradiation resulting in the formation of several species, one being a {\it c}-SiC$_2$ precursor and another being a highly polar species capable of supporting a dipole-bound electron. This strongly dipolar C$_2$Si$_2$H$_4$ isomer may represent the missing link supporting the molecular aggregation hypothesis for SiC formation. Importantly, its polarity drives molecular aggregation, and, after subsequent oxidation to C$_2$Si$_2$, its heteronuclear linkages are well-prepared for SiC nucleation, presumably initiated by a shock-wave pulsation event. Past theoretical studies by our group\footnote{Lutz J.J., Duan X.F., et al. J. Chem. Phys. 148, 174309 (2018)}\footnote{Byrd J.N., Lutz J.J., et al. J. Chem. Phys. 145, 024312 (2016)} are combined with new results, computed at the DFT and coupled-cluster levels of theory, to support the proposed mechanism

Reference Dependence of the Two-determinant Coupled-cluster Method for Triplet and Open-shell Singlet States of Biradical Molecules

We study the performance of the two-determinant (TD) coupled-cluster (CC) method which, unlike conventional ground-state single-reference (SR) CC methods, can, in principle, provide a naturally spin-adapted treatment of the lowest-lying open-shell singlet (OSS) and triplet electronic states. Various choices for the TD-CC reference orbitals are considered, including those generated by the multi-configurational self-consistent field method. Comparisons are made with the results of high-level SR-CC, equation-of-motion (EOM) CC, and multi-reference EOM calculations performed on a large test set of over 100 molecules with low-lying OSS states. It is shown that in cases where the EOMCC reference function is poorly described, TD-CC can provide a significantly better quantitative description of OSS total energies and OSS-triplet splittings

Semiconductor Color-center Structure and Excitation Spectra: Equation-of-motion Coupled-cluster Description of Vacancy and Transition-metal Defect Photoluminescence

Valence excitation spectra are computed for deep-center silicon-vacancy defects in 3C, 4H, and 6H silicon carbide (SiC), and comparisons are made with literature photoluminescence measurements. Optimizations of nuclear geometries surrounding the defect centers are performed within a Gaussian basis-set framework using many-body perturbation theory or density functional theory (DFT) methods, with computational expenses minimized by a QM/MM technique called SIMOMM. Vertical excitation energies are subsequently obtained by applying excitation-energy, electron-attached, and ionized equation-of-motion coupled-cluster (EOMCC) methods, where appropriate, as well as time-dependent (TD) DFT, to small models including only a few atoms adjacent to the defect center. We consider the relative quality of various EOMCC and TD-DFT methods for (i) energy-ordering potential ground states differing incrementally in charge and multiplicity, (ii) accurately reproducing experimentally measured photoluminescence peaks, and (iii) energy-ordering defects of different types occurring within a given polytype. The extensibility of this approach to transition-metal defects is also tested by applying it to silicon-substituted chromium defects in SiC and comparing with measurements. It is demonstrated that, when used in conjunction with SIMOMM-optimized geometries, EOMCC-based methods can provide a reliable prediction of the ground-state charge and multiplicity, while also giving a quantitative description of the photoluminescence spectra, accurate to within 0.1 eV of measurement for all cases considered. Abstract ©2018 American Physical Societ

Single-Reference Coupled Cluster Theory for Multi-Reference Problems

Coupled cluster (CC) theory is widely accepted as the most accurate and generally applicable approach in quantum chemistry. CC calculations are usually performed with single Slater-determinant references, e.g., canonical Hartree-Fock (HF) wavefunctions, though any single determinant can be used. This is an attractive feature because typical CC calculations are straightforward to apply, as there is no potentially ambiguous user input required. On the other hand, there can be concern that CC approximations give unreliable results when the reference determinant provides a poor description of the system of interest, i.e., when the HF or any other single determinant ground state has a relatively low weight in the full CI expansion. However, in many cases, the reported “failures” of CC can be attributed to an unfortunate choice of reference determinant, rather than intrinsic shortcomings of CC itself. This is connected to well-known effects like spin-contamination, wavefunction instability, and symmetry-breaking. In this contribution, a particularly difficult singlet/triplet splitting problem in two phenyldinitrene molecules is investigated, where CC with singles, doubles and perturbative triples [CCSD(T)] was reported to give poor results. This is analyzed by using different reference determinants for CCSD(T), as well as performing higher level CCSDT-3 and CCSDT calculations. We show that doubly electron attached and doubly ionized equation-of-motion (DEA/DIP-EOM) approaches are powerful alternatives for treating such systems. These are operationally single-determinant methods that adequately take the multi-reference nature of these molecules into account. Our results indicate that CC remains a powerful tool for describing systems with both static correlation and dynamic correlation, when pitfalls associated with the choice of the reference determinant are avoided

Reactions between cold methyl halide molecules and alkali-metal atoms

We investigate the potential energy surfaces and activation energies for reactions between methyl halide molecules CH3X (X = F, Cl, Br, I) and alkali-metal atoms A (A = Li, Na, K, Rb) using high-level ab initio calculations. We examine the anisotropy of each intermolecular potential energy surface (PES) and the mechanism and energetics of the only available exothermic reaction pathway, CH3X + A→CH3 + AX. The region of the transition state is explored using two-dimensional PES cuts and estimates of the activation energies are inferred. Nearly all combinations of methyl halide and alkali-metal atom have positive barrier heights, indicating that reactions at low temperatures will be slow

Predictive coupled-cluster isomer orderings for some Sin{}_nCm{}_m (m,n≤12m, n\le 12) clusters; A pragmatic comparison between DFT and complete basis limit coupled-cluster benchmarks

The accurate determination of the preferred ${\rm Si}_{12}{\rm C}_{12}$ isomer is important to guide experimental efforts directed towards synthesizing SiC nano-wires and related polymer structures which are anticipated to be highly efficient exciton materials for opto-electronic devices. In order to definitively identify preferred isomeric structures for silicon carbon nano-clusters, highly accurate geometries, energies and harmonic zero point energies have been computed using coupled-cluster theory with systematic extrapolation to the complete basis limit for set of silicon carbon clusters ranging in size from SiC$_3$ to ${\rm Si}_{12}{\rm C}_{12}$. It is found that post-MBPT(2) correlation energy plays a significant role in obtaining converged relative isomer energies, suggesting that predictions using low rung density functional methods will not have adequate accuracy. Utilizing the best composite coupled-cluster energy that is still computationally feasible, entailing a 3-4 SCF and CCSD extrapolation with triple-$\zeta$ (T) correlation, the {\it closo} ${\rm Si}_{12}{\rm C}_{12}$ isomer is identified to be the preferred isomer in support of previous calculations [J. Chem. Phys. 2015, 142, 034303]. Additionally we have investigated more pragmatic approaches to obtaining accurate silicon carbide isomer energies, including the use of frozen natural orbital coupled-cluster theory and several rungs of standard and double-hybrid density functional theory. Frozen natural orbitals as a way to compute post MBPT(2) correlation energy is found to be an excellent balance between efficiency and accuracy

Feasibility of an ED-to-Home Intervention to Engage Patients: A Mixed-Methods Investigation

Introduction: Older, chronically ill patients with limited health literacy are often under-engagedin managing their health and turn to the emergency department (ED) for healthcare needs. Wetested the impact of an ED-initiated coaching intervention on patient engagement and follow-updoctor visits in this high-risk population. We also explored patients’ care-seeking decisions. Methods: We conducted a mixed-methods study including a randomized controlled trial andindepth interviews in two EDs in northern Florida. Participants were chronically ill older EDpatients with limited health literacy and Medicare as a payer source. Patients were assignedto an evidencebased coaching intervention (n= 35) or usual post-ED care (n= 34). Qualitativeinterviews (n=9) explored patients’ reasons for ED use. We assessed average between-groupdifferences in patient engagement over time with the Patient Activation Measure (PAM) tool,using logistic regression and a difference-in-difference approach. Between-group differences infollow-up doctor visits were determined. We analyzed qualitative data using open coding andthematic analysis. Results: PAM scores fell in both groups after the ED visit but fell signi ficantly more in “usualcare” (average decline -4.64) than “intervention” participants (average decline -2.77) (β=1.87,p=0.043). There were no between-group differences in doctor visits. Patients described wellinformedreasons for ED visits including onset and severity of symptoms, lack of timely provideraccess, and immediate and comprehensive ED care. Conclusion: The coaching intervention significantly reduced declines in pati ent engagementobserved after usual post-ED care. Patients reported well-informed reasons for ED use andwill likely continue to make ED visits unless strategies, such as ED-initiated coaching, areimplemented to help vulnerable patients better manage their health and healthcare

Scattering Theory of Kondo Mirages and Observation of Single Kondo Atom Phase Shift

We explain the origin of the Kondo mirage seen in recent quantum corral Scanning Tunneling Microscope (STM) experiments with a scattering theory of electrons on the surfaces of metals. Our theory combined with experimental data provides the first direct observation of a single Kondo atom phase shift. The Kondo mirage at the empty focus of an elliptical quantum corral is shown to arise from multiple electron bounces off the walls of the corral in a manner analagous to the formation of a real image in optics. We demonstrate our theory with direct quantitive comparision to experimental data.Comment: 13 pages; significant clarifications of metho