Platinum nanoparticles on the antimony-doped tin dioxide surface: Quantum-chemical modeling

The interaction of Pt₂₉ nanoparticles with pristine and reduced (110) and (100) SnO₂ surfaces doped with Sb has been modeled using the density functional theory method within the generalized gradient approximation (GGA). It has been demonstrated that the introduction of antimony contributes to dispersion of substrate particles and, in some cases, leads to an increase in the energy of interaction with platinum and to the fixation of platinum nanoparticles on the surface.     

Oxygen behavior on the platinum surface: A quantum-chemical modeling

The dissociation of molecular oxygen and the migration of O atoms over the (100) and (111) platinum crystal surfaces have been modeled by the density functional theory method within the generalized gradient approximation (GGA). It has been demonstrated that the barrier to dissociation of the dioxygen molecule on the (100) surface is lower than that on the (111) surface. Oxygen atoms migrate over the (100) surface more readily than over the (111) surface. On the basis of these data, it is suggested that the Pt(100) surface is most efficient for dioxygen activation.     

Modeling the Effect of Dimethylsulfoxide on the Energy of Interaction of Ions in Nafion-Like Membranes

Russian Journal of Physical Chemistry A - Quantum chemical modeling is performed for the distancing of lithium and ammonium cations from the –O–CF2–CF2–SO$$_{3}^{ - }$$...     

On strongly stable normal operators in Krein spaces

For bounded normal operators in Krein spaces we give a necessary and sufficient condition for strong stability. The same result for unitary operators was obtained by M.G.Krein [1] (see also [2]). For selfadjoint operators we refer to the papers of P.Jonas, H.Langer [3] and H.Langer [4].     

Ultraheavy Yukawa-bound states of fourth-generation at Large Hadron Collider

A study of bound states of the fourth-generation quarks in the range of 500?C700 GeV is presented, where the binding energies are expected to be mainly of Yukawa origin, with QCD subdominant. Near degeneracy of their masses exhibits a new ??isospin??. The production of a colour-octet, isosinglet vector meson via $q\bar q \to \omega_8$ is the most interesting. Its leading decay modes are $\pi_8^\pm W^\mp$ , $\pi_8^0Z^0$ , and constituent quark decay, with $q\bar q$ and $t\bar t'$ and $b\bar b'$ subdominant. The colour octet, isovector pseudoscalar ?? ₈ meson decays via constituent quark decay, or to Wg. This work calls for more detailed study of fourth-generation phenomena at LHC.     

Effect of non-covalent interactions in 2,5-di-Me-pyrazine-di-N-oxide - methanol – Carbon nanotube electrocatalytic system

Catalytic oxidation of methanol (MeOH) in the absence of noble metals and noble metal oxides as catalysts, and the use of metal-free materials are inexpensive and attractive process for practical use in electrocatalysis, sensors, and in direct methanol fuel cells. In previous works, it was found that the use of single-walled (SWCNT) or multi-walled (MWCNT) carbon nanotube paper electrodes instead of GC increases the catalytic efficiency of organic compounds oxidation in the presence of aromatic di-N-oxides by several times. In this work, the effect of non-covalent interactions on the catalytic efficiency of MeOH oxidation in the presence of 2,5-di-Me-pyrazine-di-N-oxide (Pyr₁) in 0.1 M Bu₄NClO₄ solution in acetonitrile at SWCNT and MWСNT paper electrodes was studied by the methods of quantum chemical modeling, Raman spectroscopy, and using electrochemical data. New factors determined the features of mechanism of MeOH oxidation on CNT electrodes and lead to an increase in the catalytic efficiency of the electrode process in comparison with the GC electrode were established.     

Simulation of proton migration pathways in phenolsulfonic acid-based membranes by B3LYP/6-31G** DFT calculations

Geometrical and energetic characteristics of clusters simulating crystal hydrates of phenolsulfonic acid (PSA) and its complexes with poly(vinyl alcohol) (PVA) and the pathways of proton transport therein were determined using the DFT (B3LYP) theory with the 6-31G** basis set. In the formation of proton-conducting PVA—PSA-based membranes, it is energetically favorable to have at least one water molecule in close proximity of the SO₃H fragment. In water-free media, the proton migration along the SO₃H group is hindered by a barrier of 30–34 kcal mol⁻¹. In the presense of water, the proton conductivity follows the relay mechanism with the activation barrier of 5–8 kcal mol⁻¹, which is close to the experimetally observed barrier of 4–6 kcal mol⁻¹. Thus, the relay mechanism of proton transfer in a sulfonic acid—water complex is energetically the most favorable. The most energetically favorable isomer is the one with the PSA and PVA fragments H-bonded through a water molecule. The deficiency of water causes the PVA OH protons to be involved in hydrogen bonding as well. The role of PVA is to align the acid molecules and participate in the relay proton transfer. Introduction of an aldehyde into the membrane results in significant improvement of its physical properties. The aldehyde reacts with the hydroxyl groups of PVA. At high humidity, one may expect little effect of the degree of cross-linking on the proton mobility.     

Activation energy of hydrogen migration by relay in the O2/Pt19/SnO2/H2 + n H2O system

In the framework of investigation of active and stable electrocatalysts for fuel cells, the hydrogen migration by relay with the consecutive formation of H₂O molecules in the O₂/Pt₁₉/SnO₂/H₂·nH₂O → O/Pt₁₉/SnO₂·nH₂O + H₂O system was simulated. The simulations were performed by the density functional theory (DFT) method with the generalized gradient adjustment (GGA=PBE) under periodic boundary conditions in the projector augmented plane wave (PAW) basis set with a pseudo-potential using the VASP program package. At the cathode on the platinum cluster surface, the oxygen molecules without a barrier form peroxide complexes that dissociate with an energy decrease. The protons transferred via the proton-conducting channels from the anode to cathode form first OH groups bound to the platinum cluster and then H₂O molecules that are easily separated from the cluster (～0.2 eV). The proton transfer process proceeds by relay and involves several water molecules.     

Theoretical study of isomerization and dissociation of acetylene dication in the ground and excited electronic states

Ab initio calculations employing the configuration interaction method including Davidson's corrections for quadruple excitations have been carried out to unravel the dissociation mechanism of acetylene dication in various electronic states and to elucidate ultrafast acetylene-vinylidene isomerization recently observed experimentally. Both in the ground triplet and the lowest singlet electronic states of C2H2(2+) the proton migration barrier is shown to remain high, in the range of 50 kcal/mol. On the other hand, the barrier in the excited 2 3A" and 1 3A' states decreases to about 15 and 34 kcal/mol, respectively, indicating that the ultrafast proton migration is possible in these states, especially, in 2 3A", even at relatively low available vibrational energies. Rice-Ramsperger-Kassel-Marcus calculations of individual reaction-rate constants and product branching ratios indicate that if C2H(2)2+ dissociates from the ground triplet state, the major reaction products should be CCH+(3Sigma-)+H+ followed by CH+(3Pi)+CH+(1Sigma+) and with a minor contribution (approximately 1%) of C2H+(2A1)+C+(2P). In the lowest singlet state, C2H+(2A1)+C+(2P) are the major dissociation products at low available energies when the other channels are closed, whereas at Eint>5 eV, the CCH+(1A')+H+ products have the largest branching ratio, up to 70% and higher, that of CH+(1Sigma+)+CH+(1Sigma+) is in the range of 25%-27%, and the yield of C2H++C+ is only 2%-3%. The calculated product branching ratios at Eint approximately 17 eV are in qualitative agreement with the available experimental data. The appearance thresholds calculated for the CCH++H+, CH++CH+, and C2H++C+ products are 34.25, 35.12, and 34.55 eV. The results of calculations in the presence of strong electric field show that the field can make the vinylidene isomer unstable and the proton elimination spontaneous, but is unlikely to significantly reduce the barrier for the acetylene-vinylidene isomerization and to render the acetylene configuration unstable or metastable with respect to proton migration.     

Activation of molecular hydrogen on platinum nanoparticles: Quantum-chemical modeling

The interaction of molecular hydrogen with platinum clusters of different size has been modeled by the density functional theory method within the generalized gradient approximation (GGA). The cluster size turns out to have little effect on the interaction energy, whereas the effect of the cluster structure is rather significant. The most efficient interaction with hydrogen is observed for clusters with a structure resembling the crystal structure of platinum metal. In such clusters, the hydrogen molecule is attached to its surface without a barrier. Configurations with the bidentate hydrogen coordination are the most stable ones. The H atoms can migrate over the cluster surface, overcoming moderate potential barriers of ∼0.3–0.4 eV.