2,845 research outputs found

    The molecular structure of gauche-1,3-butadiene: Experimental proof of non-planarity

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    International audienceThe planarity of the second stable conformer of 1,3-butadiene-the archetypal diene for the Diels-Alder reaction, in which a planar conjugated diene and a dienophile combine to form a ring-is not established. The most recent high level calculations predict the species to adopt a twisted, gauche structure due to steric interactions between the inner terminal hydrogens rather than a planar, cis structure favored by the conjugation of the doubled bonds. Here we unambiguously prove experimentally that the structure cis-1,3-butadiene is indeed gauche with a substantial dihedral angle of 34° , in excellent agreement with theory. Observation of two tunneling components indicates that the molecule undergoes facile interconversion between two equivalent enantiomeric forms. Comparison of experimentally determined structures for gauche-and trans-butadiene provides an opportunity to examine the effects of conjugation and steric interactions

    Negative-Ion Photoelectron Spectroscopy, Gas-Phase Acidity, and Thermochemistry of the Peroxyl Radicals CH_3OO and CH_3CH_2OO

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    Methyl, methyl-d3, and ethyl hydroperoxide anions (CH_3OO-, CD_3OO-, and CH_3CH_2OO-) have been prepared by deprotonation of their respective hydroperoxides in a stream of helium buffer gas. Photodetachment with 364 nm (3.408 eV) radiation was used to measure the adiabatic electron affinities:  EA[CH_3OO, X̃^2A‘‘] = 1.161 ± 0.005 eV, EA[CD_3OO, X̃^2A‘‘] = 1.154 ± 0.004 eV, and EA[CH_3CH_2OO, X̃^2A‘‘] = 1.186 ± 0.004 eV. The photoelectron spectra yield values for the term energies:  ΔE(X̃^2A‘‘−Ã^2A‘)[CH_3OO] = 0.914 ± 0.005 eV, ΔE(X̃^2A‘‘−Ã^2A‘)[CD_3OO] = 0.913 ± 0.004 eV, and ΔE(X̃^2A‘‘−Ã^2A‘)[CH_3CH_2OO] = 0.938 ± 0.004 eV. A localized RO−O stretching mode was observed near 1100 cm^(-1) for the ground state of all three radicals, and low-frequency R−O−O bending modes are also reported. Proton-transfer kinetics of the hydroperoxides have been measured in a tandem flowing afterglow−selected ion flow tube (FA-SIFT) to determine the gas-phase acidity of the parent hydroperoxides: Δ_(acid)G_(298)(CH_3OOH) = 367.6 ± 0.7 kcal mol^(-1), Δ_(acid)G_(298)(CD_3OOH) = 367.9 ± 0.9 kcal mol^(-1), and Δ_(acid)G_(298)(CH_3CH_2OOH) = 363.9 ± 2.0 kcal mol^(-1). From these acidities we have derived the enthalpies of deprotonation: Δ_(acid)H_(298)(CH_3OOH) = 374.6 ± 1.0 kcal mol^(-1), Δ_(acid)H_(298)(CD_3OOH) = 374.9 ± 1.1 kcal mol^(-1), and Δ_(acid)H_(298)(CH_3CH_2OOH) = 371.0 ± 2.2 kcal mol^(-1). Use of the negative-ion acidity/EA cycle provides the ROO−H bond enthalpies: DH_(298)(CH_3OO−H) = 87.8 ± 1.0 kcal mol^(-1), DH_(298)(CD_3OO−H) = 87.9 ± 1.1 kcal mol^(-1), and DH_(298)(CH_3CH_2OO−H) = 84.8 ± 2.2 kcal mol^(-1). We review the thermochemistry of the peroxyl radicals, CH_3OO and CH_3CH_2OO. Using experimental bond enthalpies, DH_(298)(ROO−H), and CBS/APNO ab initio electronic structure calculations for the energies of the corresponding hydroperoxides, we derive the heats of formation of the peroxyl radicals. The “electron affinity/acidity/CBS” cycle yields Δ_fH_(298)[CH_3OO] = 4.8 ± 1.2 kcal mol^(-1) and Δ_fH_(298)[CH_3CH_2OO] = −6.8 ± 2.3 kcal mol^(-1)

    The products of the thermal decomposition of CH 3

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    We have used a heated 2 cm x 1 mm SiC microtubular (mu tubular) reactor to decompose acetaldehyde: CH3CHO + DELTA --> products. Thermal decomposition is followed at pressures of 75 - 150 Torr and at temperatures up to 1700 K, conditions that correspond to residence times of roughly 50 - 100 mu sec in the mu tubular reactor. The acetaldehyde decomposition products are identified by two independent techniques: VUV photoionization mass spectroscopy (PIMS) and infrared (IR) absorption spectroscopy after isolation in a cryogenic matrix. Besides CH3CHO, we have studied three isotopologues, CH3CDO, CD3CHO, and CD3CDO. We have identified the thermal decomposition products CH3(PIMS), CO (IR, PIMS), H (PIMS), H2 (PIMS), CH2CO (IR, PIMS), CH2=CHOH (IR, PIMS), H2O (IR, PIMS), and HC=CH (IR, PIMS). Plausible evidence has been found to support the idea that there are at least three different thermal decomposition pathways for CH3CHO: Radical decomposition: CH3CHO + DELTA --> CH3 + [HCO] --> CH3 + H + CO Elimination: CH3CHO + DELTA --> H2 + CH2=C=O. Isomerization/elimination: CH3CHO + DELTA --> [CH2=CH-OH] --> HC=CH + H2O. Both PIMS and IR spectroscopy show compelling evidence for the participation of vinylidene, CH2=C:, as an intermediate in the decomposition of vinyl alchohol: CH2=CH-OH + DELTA --> [CH2=C:] + H2O --> HC=CH + H2O

    Measurement of the t t-bar production cross section in the dilepton channel in pp collisions at sqrt(s) = 7 TeV

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    The t t-bar production cross section (sigma[t t-bar]) is measured in proton-proton collisions at sqrt(s) = 7 TeV in data collected by the CMS experiment, corresponding to an integrated luminosity of 2.3 inverse femtobarns. The measurement is performed in events with two leptons (electrons or muons) in the final state, at least two jets identified as jets originating from b quarks, and the presence of an imbalance in transverse momentum. The measured value of sigma[t t-bar] for a top-quark mass of 172.5 GeV is 161.9 +/- 2.5 (stat.) +5.1/-5.0 (syst.) +/- 3.6(lumi.) pb, consistent with the prediction of the standard model.Comment: Replaced with published version. Included journal reference and DO

    Search for the standard model Higgs boson in the H to ZZ to 2l 2nu channel in pp collisions at sqrt(s) = 7 TeV

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    A search for the standard model Higgs boson in the H to ZZ to 2l 2nu decay channel, where l = e or mu, in pp collisions at a center-of-mass energy of 7 TeV is presented. The data were collected at the LHC, with the CMS detector, and correspond to an integrated luminosity of 4.6 inverse femtobarns. No significant excess is observed above the background expectation, and upper limits are set on the Higgs boson production cross section. The presence of the standard model Higgs boson with a mass in the 270-440 GeV range is excluded at 95% confidence level.Comment: Submitted to JHE

    Combined search for the quarks of a sequential fourth generation

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    Results are presented from a search for a fourth generation of quarks produced singly or in pairs in a data set corresponding to an integrated luminosity of 5 inverse femtobarns recorded by the CMS experiment at the LHC in 2011. A novel strategy has been developed for a combined search for quarks of the up and down type in decay channels with at least one isolated muon or electron. Limits on the mass of the fourth-generation quarks and the relevant Cabibbo-Kobayashi-Maskawa matrix elements are derived in the context of a simple extension of the standard model with a sequential fourth generation of fermions. The existence of mass-degenerate fourth-generation quarks with masses below 685 GeV is excluded at 95% confidence level for minimal off-diagonal mixing between the third- and the fourth-generation quarks. With a mass difference of 25 GeV between the quark masses, the obtained limit on the masses of the fourth-generation quarks shifts by about +/- 20 GeV. These results significantly reduce the allowed parameter space for a fourth generation of fermions.Comment: Replaced with published version. Added journal reference and DO

    Search for New Physics with Jets and Missing Transverse Momentum in pp collisions at sqrt(s) = 7 TeV

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    A search for new physics is presented based on an event signature of at least three jets accompanied by large missing transverse momentum, using a data sample corresponding to an integrated luminosity of 36 inverse picobarns collected in proton--proton collisions at sqrt(s)=7 TeV with the CMS detector at the LHC. No excess of events is observed above the expected standard model backgrounds, which are all estimated from the data. Exclusion limits are presented for the constrained minimal supersymmetric extension of the standard model. Cross section limits are also presented using simplified models with new particles decaying to an undetected particle and one or two jets

    Search for anomalous t t-bar production in the highly-boosted all-hadronic final state

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    A search is presented for a massive particle, generically referred to as a Z', decaying into a t t-bar pair. The search focuses on Z' resonances that are sufficiently massive to produce highly Lorentz-boosted top quarks, which yield collimated decay products that are partially or fully merged into single jets. The analysis uses new methods to analyze jet substructure, providing suppression of the non-top multijet backgrounds. The analysis is based on a data sample of proton-proton collisions at a center-of-mass energy of 7 TeV, corresponding to an integrated luminosity of 5 inverse femtobarns. Upper limits in the range of 1 pb are set on the product of the production cross section and branching fraction for a topcolor Z' modeled for several widths, as well as for a Randall--Sundrum Kaluza--Klein gluon. In addition, the results constrain any enhancement in t t-bar production beyond expectations of the standard model for t t-bar invariant masses larger than 1 TeV.Comment: Submitted to the Journal of High Energy Physics; this version includes a minor typo correction that will be submitted as an erratu

    Performance of the CMS Cathode Strip Chambers with Cosmic Rays

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    The Cathode Strip Chambers (CSCs) constitute the primary muon tracking device in the CMS endcaps. Their performance has been evaluated using data taken during a cosmic ray run in fall 2008. Measured noise levels are low, with the number of noisy channels well below 1%. Coordinate resolution was measured for all types of chambers, and fall in the range 47 microns to 243 microns. The efficiencies for local charged track triggers, for hit and for segments reconstruction were measured, and are above 99%. The timing resolution per layer is approximately 5 ns

    Measurement of the Z/gamma* + b-jet cross section in pp collisions at 7 TeV

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    The production of b jets in association with a Z/gamma* boson is studied using proton-proton collisions delivered by the LHC at a centre-of-mass energy of 7 TeV and recorded by the CMS detector. The inclusive cross section for Z/gamma* + b-jet production is measured in a sample corresponding to an integrated luminosity of 2.2 inverse femtobarns. The Z/gamma* + b-jet cross section with Z/gamma* to ll (where ll = ee or mu mu) for events with the invariant mass 60 < M(ll) < 120 GeV, at least one b jet at the hadron level with pT > 25 GeV and abs(eta) < 2.1, and a separation between the leptons and the jets of Delta R > 0.5 is found to be 5.84 +/- 0.08 (stat.) +/- 0.72 (syst.) +(0.25)/-(0.55) (theory) pb. The kinematic properties of the events are also studied and found to be in agreement with the predictions made by the MadGraph event generator with the parton shower and the hadronisation performed by PYTHIA.Comment: Submitted to the Journal of High Energy Physic
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