Intramolecular motion and isotope effects in muonium‐substituted chloroalkyl radicals

Muon irradiation of pure liquid 3‐chloropropene, CH₂=CH-CH₂Cl, yields a primary radical, \dot\mboxCH₂-CHMu-CH₂Cl, and a secondary radical, MuCH₂-\rm\dot\mboxCH-CH₂Cl. 2‐methyl‐3‐chloropropene yields only the tertiary radical, MuCH₂-\rm\dot\mboxC(CH₃)-CH₂Cl. These three chloroalkyl radicals have been characterized by μSR and μLCR, and the hyperfine coupling constants (hfcs) have been determined over a range of temperatures, either in the pure liquid precursor or in concentrated solution. The temperature variation of the hfcs has been analyzed to obtain estimates of the barrier to internal rotation about the C_\alpha-C_\beta axis for various alkyl groups, and also their minimum energy conformations, i.e. their orientations with respect to the axis of the 2p_z orbital of the unpaired electron. The tertiary radical is particularly interesting because all three methyl‐like groups, -CH₃,-CH₂Cl and -CH₂Mu, are represented. The results can be compared to electron spin resonance data for analogous radicals, to provide information on the effects of Mu substitution for H. This revised version was published online in August 2006 with corrections to the Cover Date.     

Radio-Frequency Hexamethyldisiloxane Plasma Deposition: A Comparison of Plasma- and Deposit-Chemistry

This study reports on the effect of input power to hexamethyldisiloxane (HMDSO) plasmas. The power dependence of the plasma-phase species and of the surface chemistry (of the deposits) has been investigated. Neutral and positive molecular species were detected within the plasma using mass spectrometry (MS). Secondary ion mass spectrometry (SIMS) was used to probe the molecular structure of the deposits. The elemental composition of the surface was determined by XPS and the deposition rate was monitored using a vibrating quartz crystal microbalance. Neutral and cationic molecules of mass greater than HMDSO were detected in the plasma. Their formation through ion-molecule reactions is proposed. Changes in the relative concentration of plasma-phase species follow those seen in molecular species detected at the deposit surface. Thus, we believe that the molecular structure of the deposits can be related to the species present in the plasma. While traditionally the dominant mechanism in deposit formation is assumed to be free radical combinations, we propose other possibilities involving cations with the aim of putting forward a new perspective on plasma polymerization mechanisms and thereby stimulating discussion.     

Modeling synchronization and suppression of spontaneous otoacoustic emissions using Van der Pol oscillators: effects of aspirin administration

Many of the aspects of the interaction of spontaneous otoacoustic emissions with external tones (suppression and synchronization) can be qualitatively simulated by the behavior of a single driven Van der Pol oscillator. Analytical and numerical investigations of a model of spontaneous otoacoustic emissions based on such an oscillator (with appropriate parametric changes in the nonlinear and negative damping components) lead to predictions of the nature of the changes in suppression and synchronization (frequency-locking) tuning curves when the levels of spontaneous otoacoustic emissions are modified. Observations of the suppression and synchronization of spontaneous otoacoustic emissions by external tones of different frequencies and levels were obtained while the levels of spontaneous emissions were altered by aspirin administration. Modeling an emission as a single Van der Pol oscillator qualitatively accounts for: (1) the reduction of the level of an external tone required to suppress the emission by a decibel amount equivalent to the level reduction induced by aspirin administration; (2) the broadening of the frequency-locking tuning curve of an emission whose level is reduced; and (3) the pulling of the emission frequency by an external tone. It does not account for: (1) the observed asymmetry in the slopes of the external-tone suppression curves (more gradual for frequencies of the suppressor tone higher, rather than lower, than that of the emission); and (2) the frequency pushing of the emission by an external tone.     

Crutch or Catalyst: Teachers' Beliefs and Practices Regarding Calculator use in Mathematics Instruction

This study investigated K‐12 teachers' beliefs and reported teaching practices regarding calculator use in their mathematics instruction. A survey was administered to more than 800 elementary, middle and high school teachers in a large metropolitan area to address the following questions: (a) what are the beliefs and practices of mathematics teachers regarding calculator use? and (b) how do these beliefs and practices differ among teachers in three grade bands? Factor analysis of 20 Likert scale items revealed four factors that accounted for 54% of the variance in the ratings. These factors were named Catalyst Beliefs, Teacher Knowledge, Crutch Beliefs, and Teacher Practices. Compared to elementary teachers, high school teachers were significantly higher in their perception of calculator use as a catalyst in mathematics instruction. However, the higher the grade level of the teacher, the higher the mean score on the perception that calculator use may be a way of getting answers without understanding mathematical processes. The mean scores for teachers in all three grade bands indicated agreement that students can learn mathematics through calculator use and using calculators in instruction will lead to better student understanding and make mathematics more interesting. The survey results shed light on teachers' self reported beliefs, knowledge, and practices in regard to consistency with elements of the National Council of Teachers of Mathematics Principles and Standards for School Mathematics (2000) technology principle and the NCTM use of technology position paper (2003). This study extended previous research on teachers' beliefs regarding calculator use in classrooms by examining and comparing the results of teacher surveys across three grade bands.     

QCD corrections to the forward-backward asymmetries of c and b quarks at the Z pole

Measurements of the forward-backward production asymmetry of heavy quarks in Z decays provide a precise determination of . The asymmetries are sensitive to QCD effects, in particular hard gluon radiation. In this paper QCD corrections for and are discussed. The interplay between the experimental techniques used to measure the asymmetries and the QCD effects is investigated using simulated events. A procedure to estimate the correction needed for experimental measurements is proposed, and some specific examples are given. Received: 26 February 1998 / Published online: 2 June 1998     

Crystal structures of dimethylsuccinate and dimethyloxalate: Carbonyl group orientation for C13 chemical shielding tensor studies

The crystal structures of dimethylsuccinate (DMS) and dimethyloxalate (DMO) have been determined to facilitate the determination of the C-13 chemical shielding tensors of the carbonyl carbon in esters. Crystals of DMS are monoclinic, space groupC2/c,Z=4,a=13.154(4),b=6.156(1),c=9.363(4)Å,=98.53(3)°. The structure was solved by direct methods and refined by leastsquares procedures to giveR=0.071 for 932 observed data. Crystals of DMO are monoclinic space group,P2₁/n,Z=2, witha=3.891(1),b=11.879(2),c=6.213(2) Å,=103.32(2)°. The structure is the same (within experimental error) as that reported by Dougill and Jeffrey (1953) and refined to giveR=0.074 for 395 observed data.