Theoretical Study of the Pyrolysis of Methyltrichlorosilane in the Gas Phase. 1. Thermodynamics

Structures and energies of the gas-phase species produced during and after the various unimolecular decomposition reactions of methyltrichlorosilane (MTS) with the presence of H2 carrier gas were determined using second-order perturbation theory (MP2). Single point energies were obtained using singles + doubles coupled cluster theory, augmented by perturbative triples, CCSD(T). Partition functions were obtained using the harmonic oscillator-rigid rotor approximation. A 114-reaction mechanism is proposed to account for the gas-phase chemistry of MTS decompositions. Reaction enthalpies, entropies, and Gibbs free energies for these reactions were obtained at 11 temperatures ranging from 0 to 2000 K including room temperature and typical chemical vapor deposition (CVD) temperatures. Calculated and experimental thermodynamic properties such as heat capacities and entropies of various species and reaction enthalpies are compared, and theory is found to provide good agreement with experiment

Breaking Bonds of Open-Shell Species with the Restricted Open-Shell Size Extensive Left Eigenstate Completely Renormalized Coupled-Cluster Method

The recently developed restricted open-shell, size extensive, left eigenstate, completely renormalized (CR), coupled-cluster (CC) singles (S), doubles (D), and noniterative triples (T) approach, termed CR-CC(2,3) and abbreviated in this paper as ROCCL, is compared with the unrestricted CCSD(T) [UCCSD(T)] and multireference second-order perturbation theory (MRMP2) methods to assess the accuracy of the calculated potential energy surfaces (PESs) of eight single bond-breaking reactions of open-shell species that consist of C, H, Si, and Cl; these types of reactions are interesting because they account for part of the gas-phase chemistry in the silicon carbide chemical vapor deposition. The full configuration interaction (FCI) and multireference configuration interaction with Davidson quadruples correction [MRCI(Q)] methods are used as benchmark methods to evaluate the accuracy of the ROCCL, UCCSD(T), and MRMP2 PESs. The ROCCL PESs are found to be in reasonable agreement with the corresponding FCI or MRCI(Q) PESs in the entire region R = 1−3Re for all of the studied bond-breaking reactions. The ROCCL PESs have smaller nonparallelity error (NPE) than the UCCSD(T) ones and are comparable to those obtained with MRMP2. Both the ROCCL and UCCSD(T) PESs have significantly smaller reaction energy errors (REE) than the MRMP2 ones. Finally, an efficient strategy is proposed to estimate the ROCCL/cc-pVTZ PESs using an additivity approximation for basis set effects and correlation corrections

Detecting shapes in noise: tuning characteristics of global shape mechanisms.

The proportion of signal elements embedded in noise needed to detect a signal is a standard tool for investigating motion perception. This paradigm was applied to the shape domain to determine how local information is pooled into a global percept. Stimulus arrays consisted of oriented Gabor elements that sampled the circumference of concentric radial frequency (RF) patterns. Individual Gabors were oriented tangentially to the shape (signal) or randomly (noise). In different conditions, signal elements were located randomly within the entire array or constrained to fall along one of the concentric contours. Coherence thresholds were measured for RF patterns with various frequencies (number of corners) and amplitudes ("sharpness" of corners). Coherence thresholds (about 10% = 15 elements) were lowest for circular shapes. Manipulating shape frequency or amplitude showed a range where thresholds remain unaffected (frequency ≤ RF4; amplitude ≤ 0.05). Increasing either parameter caused thresholds to rise. Compared to circles, thresholds increased by approximately four times for RF13 and five times for amplitudes of 0.3. Confining the signals to individual contours significantly reduced the number of elements needed to reach threshold (between 4 and 6), independent of the total number of elements on the contour or contour shape. Finally, adding external noise to the orientation of the elements had a greater effect on detection thresholds than adding noise to their position. These results provide evidence for a series of highly sensitive, shape-specific analysers which sum information globally but only from within specific annuli. These global mechanisms are tuned to position and orientation of local elements from which they pool information. The overall performance for arrays of elements can be explained by the sensitivity of multiple, independent concentric shape detectors rather than a single detector integrating information widely across space (e.g. Glass pattern detector)

Breaking Bonds with the Left Eigenstate Completely Renormalized Coupled-Cluster Method

The recently developed [P. Piecuch and M. Wloch, J. Chem. Phys.123, 224105 (2005)] size-extensive left eigenstate completely renormalized (CR) coupled-cluster (CC) singles (S), doubles (D), and noniterative triples (T) approach, termed CR-CC(2,3) and abbreviated in this paper as CCL, is compared with the full configuration interaction (FCI) method for all possible types of single bond-breaking reactions between C, H, Si, and Cl (except H2) and the H2SiSiH2 double bond-breaking reaction. The CCL method is in excellent agreement with FCI in the entire region R=1–3Re for all of the studied single bond-breaking reactions, whereR and Re are the bond distance and the equilibrium bond length, respectively. The CCL method recovers the FCI results to within approximately 1mhartree in the region R=1–3Reof the H–SiH3, H–Cl, H3Si–SiH3, Cl–CH3, H–CH3, and H3C–SiH3bonds. The maximum errors are −2.1, 1.6, and 1.6mhartree in the R=1–3Re region of the H3C–CH3, Cl–Cl, and H3Si–Clbonds, respectively, while the discrepancy for the H2SiSiH2 double bond-breaking reaction is 6.6 (8.5)mhartree at R=2(3)Re. CCL also predicts more accurate relative energies than the conventional CCSD and CCSD(T) approaches, and the predecessor of CR-CC(2,3) termed CR-CCSD(T)

A Dusty Mg~II absorber Associated with the Quasar SDSS J003545.13+011441.2

We report on a dusty Mg~II absorber associated with the quasar SDSSJ003545.13+011441.2 (hereafter J0035+0114) at $z$=1.5501, which is the strongest one among the three Mg~II absorbers along the sight line of quasar. The two low redshift intervening absorbers are at $z$=0.7436, 0.5436, respectively. Based on the photometric and spectroscopic data of Sloan Digital Sky Survey (hereafter SDSS), we infer the rest frame color excess E(\bv) due to the associated dust is more than 0.07 by assuming a Small Magellanic Cloud (hereafter SMC) type extinction curve. Our follow-up moderate resolution spectroscopic observation at the 10-m Keck telescope with the ESI spectrometer enable us to reliably identify most of the important metal elements, such as Zn, Fe, Mn, Mg, Al, Si, Cr, and Ni in the associated system. We measure the column density of each species and detect significant dust depletion. In addition, we develop a simulation technique to gauge the significance of 2175-{\AA} dust absorption bump on the SDSS quasar spectra. By using it, we analyze the SDSS spectrum of J0035+0114 for the presence of a associated 2175-{\AA} extinction feature and report a tentative detection at $\sim$2$\sigma$ significant level.Comment: 24 Pages, 8 Figures, 4 Tables; Published on Ap

A generalization of the q-Saalschutz sum and the Burge transform

A generalization of the q-(Pfaff)-Saalschutz summation formula is proved. This implies a generalization of the Burge transform, resulting in an additional dimension of the ``Burge tree''. Limiting cases of our summation formula imply the (higher-level) Bailey lemma, provide a new decomposition of the q-multinomial coefficients, and can be used to prove the Lepowsky and Primc formula for the A_1^{(1)} string functions.Comment: 18 pages, AMSLaTe

A free-standing graphene-polypyrrole hybrid paper via electropolymerization with an enhanced areal capacitance

Here we developed a free-standing reduced graphene oxide (rGO)-polypyrrole (PPy) hybrid paper via electropolymerization on a paper-like graphene gel. This flexible hybrid paper displayed a uniform layered structure with PPy coated onto the graphene layers. A high areal mass of 2.7 mg cm−2 could be obtained. It delivered a greatly enhanced areal capacitance of 440 mF cm−2 at 0.5 A g−1, in contrast to that 151∼198.5 mF cm−2 previously reported for graphene paper or polypyrrole-graphene paper. It can retain ∼81% of the initial capacitance at a high current density of 6 A g−1. The combined high flexibility with outstanding electrochemical performance, makes such novel hybrid paper a promising electrode for flexible supercapacitors

Toward biodegradable Mg-air bioelectric batteries composed of silk fibroin-polypyrrole film

Biodegradable active implantable devices can be used to diagnose and/or treat disease and eventually disappear without surgical removal. If an external energy source is required for effective operation then a biocompatible and biodegradable battery would be ideal. In this study, a partially biodegradable Mg-air bioelectric battery (biobattery) is demonstrated using a silk fibroin-polypyrrole (SF-PPy) film cathode coupled with bioresorbable Mg alloy anode in phosphate buffered saline (PBS) electrolyte. PPy is chemically coated onto one side of the silk substrate. SF-PPy film shows a conductivity of ≈1.1 S cm−1 and a mild catalytic activity toward oxygen reduction. It degrades in a concentrated buffered protease XIV solution, with a weight loss of 82% after 15 d. The assembled Mg-air biobattery exhibits a discharge capacity up to 3.79 mA h cm−2 at a current of 10 μA cm−2 at room temperature, offering a specific energy density of ≈4.70 mW h cm−2. This novel partially biodegradable battery provides another step along the route to biodegradable batteries

A robust free-standing MoS2/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) film for supercapacitor applications

Two-dimensional molybdenum disulfide (MoS2) is a promising energy storage material due to its high surface area and unique electronic structure. Free-standing flexible MoS2-based electrode is of importance for use in flexible energy storage devices, whereas there are limited reports available. In this work we developed a robust hybrid film, MoS2 incorporated with highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate). This free-standing film possesses excellent mechanical properties with a fracture strength of 18.0 MPa and a Young\u27s modulus of 2.0 GPa. It can deliver a large volumetric capacitance of 141.4 F cm-3, a high volumetric energy density of 4.9 mWh cm-3, and a capacitance retention rate of 98.6% after 5000 charge/discharge cycles. This film has demonstrated its application in an all-solid-state bendable supercapacitor as well

A robust free-standing MoS2/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) film for supercapacitor applications

Two-dimensional molybdenum disulfide (MoS2) is a promising energy storage material due to its high surface area and unique electronic structure. Free-standing flexible MoS2-based electrode is of importance for use in flexible energy storage devices, whereas there are limited reports available. In this work we developed a robust hybrid film, MoS2 incorporated with highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate). This free-standing film possesses excellent mechanical properties with a fracture strength of 18.0 MPa and a Young\u27s modulus of 2.0 GPa. It can deliver a large volumetric capacitance of 141.4 F cm-3, a high volumetric energy density of 4.9 mWh cm-3, and a capacitance retention rate of 98.6% after 5000 charge/discharge cycles. This film has demonstrated its application in an all-solid-state bendable supercapacitor as well