Quantum Mechanical Treatment of Variable Molecular Composition: From "Alchemical" Changes of State Functions to Rational Compound Design

"Alchemical" interpolation paths, i.e.~coupling systems along fictitious paths that without realistic correspondence, are frequently used within materials and molecular modeling and simulation protocols for the estimation of relative changes in state functions such as free energies. We discuss alchemical changes in the context of quantum chemistry, and present illustrative numerical results for the changes of HOMO eigenvalues of the He atom due to a linear alchemical teleportation---the simultaneous annihilation and creation of nuclear charges at different locations. To demonstrate the predictive power of alchemical first order derivatives (Hellmann-Feynman) the covalent bond potential of hydrogen fluoride and hydrogen chloride is investigated, as well as the van-der-Waals binding in the water-water and water-hydrogen fluoride dimer, respectively. Based on converged electron densities for one configuration, the versatility of alchemical derivatives is exemplified for the screening of entire binding potentials with reasonable accuracy. Finally, we discuss constraints for the identification of non-linear coupling potentials for which the energy's Hellmann-Feynman derivative will yield accurate predictions

Density Functional Study of Ternary Topological Insulator Thin Films

Using an ab-initio density functional theory based electronic structure method with a semi-local density approximation, we study thin-film electronic properties of two topological insulators based on ternary compounds of Tl (Thallium) and Bi (Bismuth). We consider TlBiX$_2$ (X=Se, Te) and Bi$_2$$X$_2$Y (X,Y= Se,Te) compounds which provide better Dirac cones, compared to the model binary compounds Bi$_2$X$_3$ (X=Se, Te). With this property in combination with a structurally perfect bulk crystal, the latter ternary compound has been found to have improved surface electronic transport in recent experiments. In this article, we discuss the nature of surface states, their locations in the Brillouin zone and their interactions within the bulk region. Our calculations suggest a critical thin film thickness to maintain the Dirac cone which is significantly smaller than that in binary Bi-based compounds. Atomic relaxations or rearrangements are found to affect the Dirac cone in some of these compounds. And with the help of layer-projected surface charge densities, we discuss the penetration depth of the surface states into the bulk region. The electronic spectrum of these ternary compounds agrees very well with the available experimental results.Comment: 9 pages, 11 figures, 1 table, Accepted for publication in Physical Review

Alchemical normal modes unify chemical space

In silico design of new molecules and materials with desirable quantum properties by high-throughput screening is a major challenge due to the high dimensionality of chemical space. To facilitate its navigation, we present a unification of coordinate and composition space in terms of alchemical normal modes (ANMs) which result from second order perturbation theory. ANMs assume a predominantly smooth nature of chemical space and form a basis in which new compounds can be expanded and identified. We showcase the use of ANMs for the energetics of the iso-electronic series of diatomics with 14 electrons, BN doped benzene derivatives (C$_{6-2x}$(BN)$_{x}$H$_6$ with $x = 0, 1, 2, 3$), predictions for over 1.8 million BN doped coronene derivatives, and genetic energy optimizations in the entire BN doped coronene space. Using Ge lattice scans as reference, the applicability ANMs across the periodic table is demonstrated for III-V and IV-IV-semiconductors Si, Sn, SiGe, SnGe, SiSn, as well as AlP, AlAs, AlSb, GaP, GaAs, GaSb, InP, InAs, and InSb. Analysis of our results indicates simple qualitative structure property rules for estimating energetic rankings among isomers. Useful quantitative estimates can also be obtained when few atoms are changed to neighboring or lower lying elements in the periodic table. The quality of the predictions often increases with the symmetry of system chosen as reference due to cancellation of odd order terms. Rooted in perturbation theory the ANM approach promises to generally enable unbiased compound exploration campaigns at reduced computational cost

Pressure-Induced Rotational Symmetry Breaking in URu2_2Si2_2

Phase transitions and symmetry are intimately linked. Melting of ice, for example, restores translation invariance. The mysterious hidden order (HO) phase of URu$_2$Si$_2$ has, despite relentless research efforts, kept its symmetry breaking element intangible. Here we present a high-resolution x-ray diffraction study of the URu$_2$Si$_2$ crystal structure as a function of hydrostatic pressure. Below a critical pressure threshold $p_c\approx3$ kbar, no tetragonal lattice symmetry breaking is observed even below the HO transition $T_{HO}=17.5$ K. For $p>p_c$, however, a pressure-induced rotational symmetry breaking is identified with an onset temperatures $T_{OR}\sim 100$ K. The emergence of an orthorhombic phase is found and discussed in terms of an electronic nematic order that appears unrelated to the HO, but with possible relevance for the pressure-induced antiferromagnetic (AF) phase. Existing theories describe the HO and AF phases through an adiabatic continuity of a complex order parameter. Since none of these theories predicts a pressure-induced nematic order, our finding adds an additional symmetry breaking element to this long-standing problem.Comment: 6 pages, 4 figures and supplemental material

Removal of nitrogen from anaerobically digested swine wastewater using an anoxic/oxic (A/O) process complemented with a sulfur-packed biofilter

A modified lab-scale anoxic/oxic process was designed incorporating an upflow sulfur-packed biofilter for the treatment of anaerobically digested swine wastewater. In this study, chemical oxygen demand (COD), NH4+-N and NOx--N removal efficiencies were investigated. The experimental results showed that by increasing the internal recycle ratio from 1 to 3, the overall performance of the system improved. Organics removal efficiency was found to be fairly high and stable and the average total chemical oxygen demand (TCOD) removal efficiency ranged from 79 to 90%. This process removed up to 98% of the total NH4+-N from the nitrification reactor with proper pH control using excess alkalinity and a recycle ratio of 3. The average removal efficiency of NOx--N in the anoxic reactor was above 80% with the poor effluent quality (25 mg/l). This high concentration of NOx--N in the effluent of the anoxic reactor was removed by the sulfur-packed biofilter with the stable effluent concentrations between 0.4 and 4mg/l. This result indicates that the sulfur-packed biofilter would be used as an efficient option for denitrification by autotrophic denitrifiers during swine wastewater treatment.Key words: Biological nitrogen removal, nitrification, denitrification, chemical oxygen demand (COD), intermittent aeration, sulfur-packed bed reactor, swine wastewater, anoxic-oxic process, internal recycle

Self-optimization of optical confinement in ultraviolet photonic crystal slab laser

We studied numerically and experimentally the effects of structural disorder on the performance of ultraviolet photonic crystal slab lasers. Optical gain selectively amplifies the high-quality modes of the passive system. For these modes, the in-plane and out-of-plane leakage rates may be automatically balanced in the presence of disorder. The spontaneous optimization of in-plane and out-of-plane confinement of light in a photonic crystal slab may lead to a reduction of the lasing threshold.Comment: 5 pages, 5 figure

Ultrahigh-Q mechanical oscillators through optical trapping

Rapid advances are being made toward optically cooling a single mode of a micro-mechanical system to its quantum ground state and observing quantum behavior at macroscopic scales. Reaching this regime in room-temperature environments requires a stringent condition on the mechanical quality factor $Q_m$ and frequency $f_m$, $Q_{m}f_{m}{\gtrsim}k_{B}T_{{bath}}/h$, which so far has been marginally satisfied only in a small number of systems. Here we propose and analyze a new class of systems that should enable unprecedented $Q_{m}f_m$ values. The technique is based upon using optical forces to "trap" and stiffen the motion of a tethered mechanical structure, thereby freeing the resultant mechanical frequencies and decoherence rates from underlying material properties.Comment: 23 pages, 5 figure