Do We Need to Analyze Spectra by Hand?

Computational chemistry uses computer science to explore structures and energies of chemical species. A typical computational chemistry output file contains tens or hundreds of thousands of text lines. Automation makes the analysis of these large data sets increasingly more efficient. In turn, we constructed computer programs using Python that allow us to focus our time upon the chemical interpretation of these results. We used these efficient analyses to study a vanadiumoxo species synthesized by our collaborators. Our calculations answer many questions about the redox states in these compounds, though they predict that the experimental crystal structure may not reveal all species present. Subsequently, in an effort to distinguish which species are present, we simulated the absorption spectra of the lowest energy structures. These spectra motivated a spectral analysis program written in Mathematica, with which we gain greater insight into why these compounds absorb light differently

How Does BBr\u3csub\u3e3\u3c/sub\u3e Cyclize \u3ci\u3eo\u3c/i\u3e-Alkynylanisoles to Form Benzofurans?

Nature provides us with a wide array of chemicals that have beneficial uses. Cyclization reactions are important in the man-made creation of these chemicals. Past research by S3 scholar Samantha Ellis in Prof. Korich\u27s lab showed an unexpected cyclization reaction with o-alkynylanisoles in the presence of BBr3 instead of the expected ether cleavage reaction. We sought to understand this unusual reactivity using computational chemistry by comparing the energies of these competing pathways. However, we discovered that previously considered mechanisms for BBr3 assisted ether cleavage are incomplete. In this work we present an alternative mechanism for ether cleavage that has implications in a number of different reactions involving boron-containing reagents

Ether Cleavage Re-Investigated: Elucidating the Mechanism of BBr3- Facilitated Demethylation of Aryl Methyl Ethers

Boron tribromide is a versatile reagent utilized in diverse areas ranging from polymer chemistry to natural product synthesis.[1] Owing its high reactivity to the Lewis acidic boron center, BBr3 reactions include haloborylation,[2] boron–silicon exchange,[3] and rearrangement of 7,7-diphenylhydromorphone derivatives.[4] While there is no shortage in the diversity of BBr3-mediated reactions, many of the mechanisms for these transformations have not been fully elucidated. In this report we investigate the mechanism of ether cleavage by BBr3 [5–10] in anisole. Conceptually, demethylation of anisole is initiated by the formation of an ether adduct 1 followed by the loss of bromide. Free bromide nucleophilically attacks the methyl group of the cationic intermediate (2) cleaving the C–O bond and producing PhOBBr2, which undergoes hydrolysis upon aqueous work-up. While this pathway (Scheme 1) at first appears to be viable, we calculated that the formation of 2 and bromide in dichloromethane is thermodynamically inaccessible (ΔG = +38.9 kcal/mol). Recently, alternative mechanisms for ether cleavage were proposed by Sousa and Silva that involve unimolecular or bimolecular rate-determining steps that circumvent formation of bromide in solution (Scheme 2).[11] While a unimolecular process is kinetically favored for ethers containing one or more substituents (e.g. branched alkyl) that stabilize carbocation character in an SN1-like transition state, this barrier for demethylation of primary C atoms, like in the methyl group of anisole, lies too high on the potential energy surface to be accessible under reported reaction conditions. They found that a bimolecular process (Scheme 2, bottom) decreases the kinetic barrier for anisole demethylation significantly. During this reaction pathway, one of the bromides of the first ether adduct nucleophilically attacks the methyl group of the second ether adduct. This is analogous to an SN2 reaction with 180o attack of the methyl group by a bromide in the nucleophilic ether adduct. However, this bimolecular pathway produces two highly charged intermediates 2 and 3 that Sousa and Silva did not investigate. Their computational investigation stopped with the calculation of the initial kinetic barrier.[11] We speculate that these charged intermediates may undergo a similar bimolecular reaction to yield two equivalents of PhOBBr2 and MeBr. Moreover, if charged intermediates are formed then we believe an important set of mechanistic pathways may have been overlooked, namely, those where Lewis acidic BBr3 abstracts bromide from the ether complex to form BBr4 – in a mechanism related to the pathway introduced in Scheme 1

Onset of Wave Drag due to Generation of Capillary-Gravity Waves by a Moving Object as a Critical Phenomenon

The onset of the {\em wave resistance}, via generation of capillary gravity waves, of a small object moving with velocity $V$, is investigated experimentally. Due to the existence of a minimum phase velocity $V_c$ for surface waves, the problem is similar to the generation of rotons in superfluid helium near their minimum. In both cases waves or rotons are produced at $V>V_c$ due to {\em Cherenkov radiation}. We find that the transition to the wave drag state is continuous: in the vicinity of the bifurcation the wave resistance force is proportional to $\sqrt{V-V_c}$ for various fluids.Comment: 4 pages, 7 figure

A Series of 4- and 5-Coordinate Ni(II) Complexes: Synthesis, Characterization, Spectroscopic, and DFT Studies

A series of four- and five-coordinate Ni(II) complexes CztBu(PyriPr)2NiX (1–3 and 1·THF–3·THF), where X = Cl, Br, and I, were synthesized and fully characterized by NMR and UV–vis spectroscopy, X-ray crystallography, cyclic voltammetry, and density functional theory calculations. The solid-state structures of 1–3 reveal rare examples of seesaw Ni(II) complexes. In solution, 1–3 bind reversibly to a THF molecule to form five-coordinate adducts. The electronic transitions in the visible region (630–680 nm), attributed to LMCT bands, for 1 → 3 exhibit a bathochromic shift. The thermochromic tendency of the five-coordinate complexes implies the loss of THF coordination at elevated temperatures. Finally, the electronic properties of all Ni(II) complexes were studied by time-dependent density functional theory calculations to characterize the nature of the excited states

The Eastern Arm of M83 Revisited: High-Resolution Mapping of 12CO 1-0 Emission

We have used the Owens Valley Millimeter Array to map 12CO (J=1-0) along a 3.5 kpc segment of M83's eastern spiral arm at resolutions of 6.5"x3.5", 10", and 16". The CO emission in most of this segment lies along the sharp dust lane demarking the inner edge of the spiral arm, but beyond a certain point along the arm the emission shifts downstream from the dust lane to become better aligned with the young stars seen in blue and H-beta images. This morphology resembles that of the western arm of M100. Three possibilities, none of which is wholly satisfactory, are considered to explain the deviation of the CO arm from the dust lane: heating of the CO by UV radiation from young stars, heating by low-energy cosmic rays, and a molecular medium consisting of two (diffuse and dense) components which react differently to the density wave. Regardless, the question of what CO emission traces along this spiral arm is a complicated one. Strong tangential streaming is observed where the arm crosses the kinematic major axis of the galaxy, implying that the shear becomes locally prograde in the arms. Inferred from the streaming is a very high gas surface density of about 230 solar masses/pc**2 and an arm-interarm contrast greater than 2.3 in the part of the arm near the major axis. Using two different criteria, we find that the gas at this location is well above the threshold for gravitational instability -- much more clearly so than in either M51 or M100.Comment: Accepted for publication in ApJ. 25 pages, 5 figures. Manuscript in LaTeX, figures in pdf. Fig 3 in colo

Formal analytical solutions for the Gross-Pitaevskii equation

Considering the Gross-Pitaevskii integral equation we are able to formally obtain an analytical solution for the order parameter $\Phi (x)$ and for the chemical potential $\mu$ as a function of a unique dimensionless non-linear parameter $\Lambda$. We report solutions for different range of values for the repulsive and the attractive non-linear interactions in the condensate. Also, we study a bright soliton-like variational solution for the order parameter for positive and negative values of $\Lambda$. Introducing an accumulated error function we have performed a quantitative analysis with other well-established methods as: the perturbation theory, the Thomas-Fermi approximation, and the numerical solution. This study gives a very useful result establishing the universal range of the $\Lambda$-values where each solution can be easily implemented. In particular we showed that for $\Lambda <-9$, the bright soliton function reproduces the exact solution of GPE wave function.Comment: 8 figure

Getting the right balance: insole design alters the static balance of people with diabetes and neuropathy

BACKGROUND: Over 1 in 3 older people with diabetes sustain a fall each year. Postural instability has been identified as independent risk factor for falls within people with Diabetic Peripheral Neuropathy (DPN). People with DPN, at increased risk of falls, are routinely required to wear offloading insoles, yet the impact of these insoles on postural stability and postural control is unknown. The aim of this study was to evaluate the effect of a standard offloading insole and its constituent parts on the balance in people with DPN. METHODS: A random sample of 50 patients with DPN were observed standing for 3 × 30 s, and stepping in response to a light, under five conditions presented in a random order; as defined by a computer program; 1) no insole, 2) standard diabetic: a standard offloading insole made from EVA/poron®, and three other insoles with one design component systematically altered 3) flat: diabetic offloading insole with arch fill removed, 4) low resilient memory: diabetic offloading insole with the cover substituted with low resilience memory V9, 5) textured: diabetic offloading insole with a textured PVC surface added (Algeos Ltd). After each condition participants self-rated perceived steadiness. RESULTS: Insole design effected static balance and balance perception, but not stepping reaction time in people with DPN. The diabetic and memory shaped insoles (with arch fill) significantly increased centre of pressure velocity (14 %, P = 0.006), (13 %, P = 0.001), and path length (14 %, P = 0.006), (13 %, P = 001), when compared to the no insole condition. The textured shaped and flat soft insole had no effect on static balance when compared to the no insole condition (P > 0.05). CONCLUSION: Insoles have an effect on static balance but not stepping reaction time. This effect is independent of neuropathy severity. The addition of a textured cover seems to counter the negative effect of an arch fill, even in participants with severe sensation loss. Static balance is unaffected by material softness or resilience. Current best practice of providing offloading insoles, with arch fill, to increase contact area and reduce peak pressure could be making people more unstable. Whilst flat, soft insoles maybe the preferable design option for those with poor balance. There is a need to develop an offloading insole that can reduce diabetic foot ulcer risk, without compromising balance