Reliable and efficient reaction path and transition state finding for surface reactions with the growing string method

The computational challenge of fast and reliable transition state and reaction path optimization requires new methodological strategies to maintain low cost, high accuracy, and systematic searching capabilities. The growing string method using internal coordinates has proven to be highly effective for the study of molecular, gas phase reactions, but difficulties in choosing a suitable coordinate system for periodic systems has prevented its use for surface chemistry. New developments are therefore needed, and presented herein, to handle surface reactions which include atoms with large coordination numbers that cannot be treated using standard internal coordinates. The double‐ended and single‐ended growing string methods are implemented using a hybrid coordinate system, then benchmarked for a test set of 43 elementary reactions occurring on surfaces. These results show that the growing string method is at least 45% faster than the widely used climbing image‐nudged elastic band method, which also fails to converge in several of the test cases. Additionally, the surface growing string method has a unique single‐ended search method which can move outward from an initial structure to find the intermediates, transition states, and reaction paths simultaneously. This powerful explorative feature of single ended‐growing string method is demonstrated to uncover, for the first time, the mechanism for atomic layer deposition of TiN on Cu(111) surface. This reaction is found to proceed through multiple hydrogen‐transfer and ligand‐exchange events, while formation of H‐bonds stabilizes intermediates of the reaction. Purging gaseous products out of the reaction environment is the driving force for these reactions. © 2017 Wiley Periodicals, Inc.     

Residual stress field and reduction of stress intensity factors in cold-worked holes

Closed-form and semi-analytical solutions are obtained for the residual stress distributions in a plate caused by pressure acting on a central circular hole, representing the cold-work process. The material is elastic–perfectly plastic. Both Tresca and von Mises yield criteria are used and the corresponding residual stress distributions are compared. The relation between the dimension of the plastic zone and the value of internal pressure is presented. The relation between the magnitude of the residual stresses and the remote uniform tensile stress required to open symmetrical radial cracks is also presented. The reduction of the stress intensity factors of cracked open and riveted holes as a function of the internal pressure applied (or mandrel radial displacement) is investigated using numerical models for both an elastic–perfectly plastic material and for an Al 2024-T3 Alclad aluminum alloy.     

Excited‐State Dynamics of the Metal String Complex Co3(dpa)4(NCS)2 from Femtosecond Transient Absorption Spectra

Transient absorption spectroscopy is used to study the excited‐state dynamics of Co₃(dpa)₄(NCS)₂, where dpa is the ligand di(2‐pyridyl)amido. The ππ*, charge‐transfer, and d–d transition states are excited upon irradiation at wavelengths of 330, 400 and 600 nm, respectively. Similar transient spectra are observed under the experimental temporal resolution and the transient species show weak absorption. We thus propose that a low‐lying metal‐centered d–d state is accessed immediately after excitation. Analyses of the experimental kinetic traces reveal rapid conversion from the ligand‐centered ππ* and the charge‐transfer states to this metal‐centered d‐d state within 100 fs. The excited molecule then crosses to a second d–d state within the ligand‐field manifold, with a time coefficient of 0.6–1.4 ps. Because the ground‐state bleaching band recovers with a time coefficient of 10–23 ps, we propose that an excited molecule crosses from the low‐lying d–d state either directly within the same spin system or with spin crossing via the state ²B to the ground state ²A₂ (symmetry group C₄). In this trimetal string complex, relaxation to the ground electronic surface after excitation is thus rapid.     

An interplay between static potential and Reggeon trajectory for QCD string

I consider two cases where QCD string is described by an effective theory of long strings: the static potential and meson scattering amplitudes in the Regge regime. I show how they can be solved in the mean-field approximation, justified by the large number of space–time dimensions, and argue that it turns out to be exact. I compare contributions from QCD string and perturbative QCD and discuss experimental consequences for the scattering amplitudes.     

The effect of density dependent Av18 effective interaction on the ground state properties of heavy closed shell nuclei

The channel-dependent Argonne Av₁₈ effective two-body interactions (CDEI) which are generated through the lowest order constrained variational (LOCV) calculation for asymmetric nuclear matter with the charge-dependent Av₁₈ bare nucleon–nucleon potential are used to calculate the ground state properties of heavy closed shell nuclei such as ⁴⁸Ca, ⁹⁰Zr, ¹²⁰Sn and ²⁰⁸Pb. The harmonic oscillator basis, and the local density approximation (LDA) are applied to create the relative and the center of mass dependent effective two-body potential. We get more binding with respect to the similar calculation with the Reid types potentials. It is tried to omit the LDA and perform full calculation with the Av₁₈CDEI for light nuclei. The results indicate that the LDA works quite well. It is also shown that in case of heavy closed shell nuclei and unlike our previous report with Reid68Day   interaction, the contributions of higher partial waves (J>2$J>2$) are very important for the calculations with Av₁₈ potential and we get reasonable agreement between our calculated binding energies and RMS radii, with those predicated by the others methods, and the experimental data. Finally, the various aspects of channel and density dependent two-body effective interactions are discussed.     

Fragile black holes

The AdS/CFT correspondence may give a new way of understanding field theories in extreme conditions, as in the quark–gluon plasma phase of quark matter. The correspondence normally involves asymptotically AdS black holes with dual field theories which are defined on locally flat boundary spacetimes; the implicit assumption is that the distortions of spacetime which occur under extreme conditions do not affect the field theory in any unexpected way. However, AdS black holes are [to varying degrees] fragile, in the sense that they become unstable to stringy effects when their event horizons are sufficiently distorted. This implies that field theories on curved backgrounds may likewise be unstable in a suitable sense. We investigate this phenomenon, focussing on the “fragility” of AdS₅ black holes with flat event horizons. We find that, when they are distorted, these black holes are always unstable in string theory. This may have consequences for the detailed structure of the quark matter phase diagram at extreme values of the spacetime curvature.     

Embeddable quantum homogeneous spaces

We discuss various notions generalizing the concept of a homogeneous space to the setting of locally compact quantum groups. On the von Neumann algebra level we recall an interesting duality for such objects studied earlier by M. Izumi, R. Longo, S. Popa for compact Kac algebras and by M. Enock in the general case of locally compact quantum groups. A definition of a quantum homogeneous space is proposed along the lines of the pioneering work of Vaes on induction and imprimitivity for locally compact quantum groups. The concept of an embeddable quantum homogeneous space is selected and discussed in detail as it seems to be the natural candidate for the quantum analog of classical homogeneous spaces. Among various examples we single out the quantum analog of the quotient of the Cartesian product of a quantum group with itself by the diagonal subgroup, analogs of quotients by compact subgroups as well as quantum analogs of trivial principal bundles. The former turns out to be an interesting application of the duality mentioned above.     

On Kaufmanʼs theorem

Kaufman?s theorem (Kaufman, 1978 [9]) on representing closed linear operators as quotients of bounded operators is given a new constructive proof, and is extended to operators between two Hilbert spaces. Two different definitions of operator quotients existing in the literature are compared.     

An existence theorem of Walrasian equilibrium

The purpose of this note is to establish an existence theorem for Walrasian equilibrium under weaker conditions.