Toward benchmarking theoretical computations of elementary rate constants on catalytic surfaces: formate decomposition on Au and Cu

With the emergence of methods for computing rate constants for elementary reaction steps of catalytic reactions, benchmarking their accuracy becomes important. The unimolecular dehydrogenation of adsorbed formate on metal surfaces serves as a prototype for comparing experiment and theory. Previously measured pre-exponential factors for CO₂ formation from formate on metal surfaces, including Cu(110), are substantially higher than expected from the often used value of k_BT/h, or ∼6 × 10¹² s⁻¹, suggesting that the entropy of the transition state is higher than that of the adsorbed formate. Herein, the rate constant parameters for formate decomposition on Au(110) and Cu(110) are addressed quantitatively by both experiment and theory and compared. A pre-exponential factor of 2.3 × 10¹⁴ s⁻¹ was obtained experimentally on Au(110). DFT calculations revealed the most stable configuration of formate on both surfaces to be bidentate and the transition states to be less rigidly bound to the surface compared to the reactant state, resulting in a higher entropy of activation and a pre-exponential factor exceeding k_BT/h. Though reasonable agreement is obtained between experiment and theory for the pre-exponential factors, the activation energies determined experimentally remain consistently higher than those computed by DFT using the GGA–PBE functional. This difference was largely erased when the metaGGA–SCAN functional was applied. This study provides insight into the underlying factors that result in the relatively high pre-exponential factors for unimolecular decomposition on metal surfaces generally, highlights the importance of mobility for the transition state, and offers vital information related to the direct use of DFT to predict rate constants for elementary reaction steps on metal surfaces.

The underlying factors that result in the high pre-exponential factors for formate decomposition on Au and Cu(110) surfaces and the origins of differences between experiment and theory that may arise are reported.     

Production of scalar Higgs and pseudoscalar Higgs in multi-Higgs doublet models at \gamma\gamma colliders

We present the effects of heavy CP-even (H) and CP-odd (A) Higgs bosons on the production cross section of the process at the energy around the mass poles of the Higgs bosons. It is found that interference between H and A with small mass gap, as well as the ones between Higgs bosons and continuum, contributes to the cross section, if the photon beams are polarized and if we observe the helicity of the top quarks. It is demonstrated in the framework of the minimal supersymmetric extension of the standard model that the H and A contributions can be sizable at future colliders for small values of . The methods to measure the CP-parity of the Higgs boson are also presented. The statistical significance of detecting the Higgs signals and measuring the Higgs CP-parity is evaluated. Received: 16 December 1999 / Revised version: 30 January 2000 / Published online: 6 April 2000     

Production of CP-even and CP-odd Higgs bosons at muon colliders

In the s-channel Higgs-boson exchange processes, the interference between the amplitudes for CP-even and CP-odd Higgs bosons is sizable, if the helicities of the initial and final particles are properly fixed and if the mass difference between these bosons is not much larger than their decay widths. We discuss this interference effect in the process . Examining the effect gives us information on the CP-parity for the Higgs bosons and on the sign of the product of the coupling constants for the and vertices. The feasibility of observing the interference effect in future muon colliders is evaluated in the framework of the minimal supersymmetric extension of the standard model as an example.     

Design and synthesis of artificial phospholipid for selective cleavage of integral membrane protein

An artificial phospholipid, possessing saturated alkyl chains as a membrane anchor and protein recognition site as well as an Fe(III)-EDTA moiety as a protein cleavable polar head group, was designed and synthesized based on the amidite method for the purpose of examination of cleavage of integral membrane proteins.     

Nitrite reduction on morphologically controlled Pt nanoparticles

On the surface of morphologically controlled Pt nanoparticles, statistically rich in [100] crystalline facet, nitrite ions were reduced by H2 to N2 with high selectivity.     

Generation of all-solid-state, high-power continuous-wave 213-nm light based on sum-frequency mixing in CsLiB6O10

Achievement of more than 100 mW of pure continuous-wave deep-ultraviolet radiation at 213 nm has been demonstrated in an efficient all-solid-state laser system that uses two Brewster-cut CsLiB6O10 (CLBO) crystals. The first crystal is used for 266-nm generation by external resonant doubling of 532-nm radiation from a frequency-doubled Nd:YVO4 laser. Subsequent sum-frequency mixing is performed in a second CLBO crystal placed in a diode-pumped Nd:YAG laser cavity to mix the single-pass 266-nm output with circulating 1064-nm light.     

Central pseudorapidity gaps in events with a leading antiproton at the fermilab tevatron pp collider

We report a measurement of the fraction of events with a large pseudorapidity gap deltaeta within the pseudorapidity region available to the proton dissociation products X in p+p-->p+X. For a final state p of fractional momentum loss xi(p) and 4-momentum transfer squared t(p) within 0.063 is found to be 0.246+/-0.001 (stat)+/-0.042 (syst) [0.184+/-0.001 (stat)+/-0.043 (syst)]. Our results are compared with gap fractions measured in minimum bias pp collisions and with theoretical expectations.     

Search for long-lived charged massive particles in pp collisions at square root s = 1.8 TeV

We report a search for the production of long-lived charged massive particles in a data sample of 90 pb(-1) of square root[s]=1.8 TeV pp collisions recorded by the Collider Detector at Fermilab. The search uses the muonlike penetration and anomalously high ionization energy loss signature expected for such a particle to discriminate it from backgrounds. The data are found to agree with background expectations, and cross section limits of O(1) pb are derived using two reference models, a stable quark and a stable scalar lepton.