An insertion algorithm for catabolizability

Our recent work in Blasiak (2011) [1] exhibits a canonical basis of the Garsia-Procesi module R_λ with cells labeled by standard tableaux of catabolizability ?λ. Through our study of the Kazhdan-Lusztig preorder on this basis, we found a way to transform a standard word labeling a basis element into a word inserting to the unique tableau of shape λ. This led to an algorithm that computes the catabolizability of the insertion tableau of a standard word. We deduce from this a characterization of catabolizability as the statistic on words invariant under Knuth transformations, certain (co)rotations, and a new set of transformations we call catabolism transformations. We further deduce a Greene’s Theorem-like characterization of catabolizability and a result about how cocyclage changes catabolizability, strengthening a similar result in Shimozono and Weyman (2000) [8].     

Finite element modeling of interfacial forces and contact stresses of pneumatic tire on fresh snow for combined longitudinal and lateral slips

Significant challenges exist in the prediction of interaction forces generated from the interface between pneumatic tires and snow-covered terrains due to the highly non-linear nature of the properties of flexible tires, deformable snow cover and the contact mechanics at the interface of tire and snow. Operational conditions of tire-snow interaction are affected by many factors, especially interfacial slips, including longitudinal slip during braking or driving, lateral slip (slip angle) due to turning, and combined slip (longitudinal and lateral slips) due to brake-and-turn and drive-and-turn maneuvers, normal load applied on the wheel, friction coefficient at the interface and snow depth. This paper presents comprehensive three-dimensional finite element simulations of tire-snow interaction for low-strength snow under the full-range of controlled longitudinal and lateral slips for three vertical loads to gain significant mechanistic insight. The pneumatic tire was modeled using elastic, viscoelastic and hyperelastic material models; the snow was modeled using the modified Drucker-Prager Cap material model (MDPC). The traction, motion resistance, drawbar pull, tire sinkage, tire deflection, snow density, contact pressure and contact shear stresses were obtained as a function of longitudinal slip and lateral slip. Wheel states - braked, towed, driven, self-propelled, and driving - have been identified and serve as key classifiers of discernable patterns in tire-snow interaction such as zones of contact shear stresses. The predicted results can be applied to analytical deterministic and stochastic modeling of tire-snow interaction.     

Optimal scaling factors for CM1 and CM3 atomic charges in RM1-based aqueous simulations

Scaling factors for atomic charges derived from the RM1 semiempirical quantum mechanical wavefunction in conjunction with CM1 and CM3 charge models have been optimized by minimizing errors in absolute free energies of hydration, ΔG_hyd, for a set of 40 molecules. Monte Carlo statistical mechanics simulations and free energy perturbation theory were used to annihilate the solutes in gas and in a box of TIP4P water molecules. Lennard–Jones parameters from the optimized potentials for liquid simulations‐all atom (OPLS–AA) force field were utilized for the organic compounds. Optimal charge scaling factors have been determined as 1.11 and 1.14 for the CM1R and CM3R methods, respectively, and the corresponding unsigned average errors in ΔG_hyd relative to experiment were 2.05 and 1.89 kcal/mol. Computed errors in aniline and two derivatives were particularly large for RM1 and their removal from the data set lowered the overall errors to 1.61 and 1.75 kcal/mol for CM1R and CM3R. Comparisons are made to the AM1 method which yielded total errors in ΔG_hyd of 1.50 and 1.64 kcal/mol for CM1A*1.14 and CM3A*1.15, respectively. This work is motivated by the need for a highly efficient yet accurate quantum mechanical (QM) method to study condensed‐phase and enzymatic chemical reactions via mixed QM and molecular mechanical (QM/MM) simulations. As an initial test, the Menshutkin reaction between NH₃ and CH₃Cl in water was computed using a RM1/TIP4P‐Ew/CM3R procedure and the resultant ΔG^?, ΔG_rxn, and geometries were in reasonable accord with other computational methods; however, some potentially serious shortcomings in RM1 are discussed. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011     

Surface activation of electrocatalysis at oxide electrodes. Concerted electron-proton transfer

Dramatic rate enhancements are observed for the oxidation of phenols, including tyrosine, at indium-tin oxide electrodes modified by the addition of the electron-transfer relays [M(II)(bpy)(2)(4,4'-(HO)(2)P(O)CH(2))(2)bpy)](2+) (M = Ru, Os) with clear evidence for the importance of proton-coupled electron transfer and concerted electron-proton transfer.     

Investigation of surface topology of printed nanoparticle layers using wide‐angle low‐Q scattering

A new small‐angle scattering technique in reflection geometry is described which enables a topological study of rough surfaces. This is achieved by using long‐wavelength soft X‐rays which are scattered at wide angles but in the low‐Q range normally associated with small‐angle scattering. The use of nanometre‐wavelength radiation restricts the penetration to a thin surface layer which follows the topology of the surface, while moving the scattered beam to wider angles preventing shadowing by the surface features. The technique is, however, only applicable to rough surfaces for which there is no specular reflection, so that only the scattered beam was detected by the detector. As an example, a study of the surfaces of rough layers of silicon produced by the deposition of nanoparticles by blade‐coating is presented. The surfaces of the blade‐coated layers have rough features of the order of several micrometers. Using 2 nm and 13 nm X‐rays scattered at angular ranges of 5°≤θ≤ 51° and 5°≤θ≤ 45°, respectively, a combined range of scattering vector of 0.00842 Å^?1≤Q≤ 0.4883 Å^?1 was obtained. Comparison with previous transmission SAXS and USAXS studies of the same materials indicates that the new method does probe the surface topology rather than the internal microstructure.     

Slip-based experimental studies of a vehicle interacting with natural snowy terrain

As longitudinal slip affects vehicle–pavement interactions on roads and hard surfaces, so too does it play an important role in interactions between vehicles and soft terrains, including snow. Although many slip-based models have been developed recently for tire–snow interactions (e.g., [1] and references cited therein), these models have only been partially validated, due to a lack of relevant experimental data. This paper presents comprehensive data from tests that were performed using a newly-developed test vehicle traversing natural snowy terrain, over a wide range of values for longitudinal slip, vertical load and torque via an effective accelerate/brake maneuver. Drawbar pull, motion resistance, wheel states and tire stiffness were presented as a function of slip; tire sinkage was obtained using a laser profilometer; strength and depth of snow were found using a snow micropenetrometer. The effects of the rear tire going over snow compacted by the front tire were also studied. The maximum traction force normalized by the vertical load is found to be ≈0.47, maximum motion resistance normalized by the vertical load is ≈0.4. Comparison of the trend and order-of-magnitude of test results with those from existing slip-based numerical model [1] shows good comparison in motion resistance, tire sinkage, and longitudinal stiffness, but indicates that a better traction model is needed to improve the comparison.     

Self-ordering of colloidal particles in shallow nanoscale surface corrugations

The influence of nanoscale out-of-plane roughness on the ordering of submicron spheres during evaporative deposition from colloidal suspension was examined using shallow corrugated substrates possessing optical wavelengths and nanoscale amplitude. Under conditions in which spheres were embedded in a liquid layer with thickness on the order of the sphere diameter, it was observed that the spheres overwhelmingly deposited in the valleys of the surface corrugations rather than on their peaks. This behavior persisted to surprisingly shallow corrugation amplitudes, sometimes 100 times smaller than the sphere diameter. An analysis of the capillary forces on the spheres explains this behavior and also yields a critical corrugation amplitude below which a substrate will appear "flat" to depositing spheres. The observation that substrate features significantly smaller than the sphere diameter can influence deposition morphology may lead to simple methods to create large domains of order in colloidal crystals.     

Pulse radiolysis study of the reaction of OH radicals with C2H4 over the temperature range 343–1173 K

The reaction of OH and OD radicals with ethylene in the presence of 1 atm argon and 6 Torr water vapor was studied in the temperature range 343–1173 K. The results reveal three kinetically separate temperature regions: (1) 343–563 K, where the disappearance of OH radical is dominated by the addition of OH to the double bond of ethylene; (2) 563–748 K, where concurrent reactions of addition, the reverse reaction of addition and H-atom abstraction is dominant; and (3) 748–1173 K, where H-atom abstraction is likely the main reaction. The rate for hydrogen abstraction is 2.4 × 10^?11 exp[(?2104 ± 125)/T] cm³/molec-s (for OD 2.1 × 10^?11 exp[(?2130 ± 172)/T] cm³/molec-s). There was no obvious pyrolysis of ethylene below 1073 K. The study of OD radical with ethylene shows a small isotope effect.     

Picosecond pulse radiolysis of aromatic solutes in cyclohexane: formation of solute triplet states

Evolution of the absorption spectra due to transient species produced by the pulse radiolysis of biphenyl, pyrene, diphenylamine, and naphthalene in cyclohexane was measured over 50 ps to 3 ns. The initial (50 ps) yield of triplet is only a small fraction of the yield (G ≈ 0.3) at 3 ns.