Reaction rate theory: what it was, where is it today, and where is it going?

A brief history is presented, outlining the development of rate theory during the past century. Starting from Arrhenius [Z. Phys. Chem. 4, 226 (1889)], we follow especially the formulation of transition state theory by Wigner [Z. Phys. Chem. Abt. B 19, 203 (1932)] and Eyring [J. Chem. Phys. 3, 107 (1935)]. Transition state theory (TST) made it possible to obtain quick estimates for reaction rates for a broad variety of processes even during the days when sophisticated computers were not available. Arrhenius' suggestion that a transition state exists which is intermediate between reactants and products was central to the development of rate theory. Although Wigner gave an abstract definition of the transition state as a surface of minimal unidirectional flux, it took almost half of a century until the transition state was precisely defined by Pechukas [Dynamics of Molecular Collisions B, edited by W. H. Miller (Plenum, New York, 1976)], but even this only in the realm of classical mechanics. Eyring, considered by many to be the father of TST, never resolved the question as to the definition of the activation energy for which Arrhenius became famous. In 1978, Chandler [J. Chem. Phys. 68, 2959 (1978)] finally showed that especially when considering condensed phases, the activation energy is a free energy, it is the barrier height in the potential of mean force felt by the reacting system. Parallel to the development of rate theory in the chemistry community, Kramers published in 1940 [Physica (Amsterdam) 7, 284 (1940)] a seminal paper on the relation between Einstein's theory of Brownian motion [Einstein, Ann. Phys. 17, 549 (1905)] and rate theory. Kramers' paper provided a solution for the effect of friction on reaction rates but left us also with some challenges. He could not derive a uniform expression for the rate, valid for all values of the friction coefficient, known as the Kramers turnover problem. He also did not establish the connection between his approach and the TST developed by the chemistry community. For many years, Kramers' theory was considered as providing a dynamic correction to the thermodynamic TST. Both of these questions were resolved in the 1980s when Pollak [J. Chem. Phys. 85, 865 (1986)] showed that Kramers' expression in the moderate to strong friction regime could be derived from TST, provided that the bath, which is the source of the friction, is handled at the same level as the system which is observed. This then led to the Mel'nikov-Pollak-Grabert-Hanggi [Mel'nikov and Meshkov, J. Chem. Phys. 85, 1018 (1986); Pollak, Grabert, and Hanggi, ibid. 91, 4073 (1989)] solution of the turnover problem posed by Kramers. Although classical rate theory reached a high level of maturity, its quantum analog leaves the theorist with serious challenges to this very day. As noted by Wigner [Trans. Faraday Soc. 34, 29 (1938)], TST is an inherently classical theory. A definite quantum TST has not been formulated to date although some very useful approximate quantum rate theories have been invented. The successes and challenges facing quantum rate theory are outlined. An open problem which is being investigated intensively is rate theory away from equilibrium. TST is no longer valid and cannot even serve as a conceptual guide for understanding the critical factors which determine rates away from equilibrium. The nonequilibrium quantum theory is even less well developed than the classical, and suffers from the fact that even today, we do not know how to solve the real time quantum dynamics for systems with "many" degrees of freedom.     

The angular momentum controversy: What’s it all about and does it matter?

The general question, crucial to an understanding of the internal structure of the nucleon, of how to split the total angular momentum of a photon or gluon into spin and orbital contributions is one of the most important and interesting challenges faced by gauge theories like Quantum Electrodynamics and Quantum Chromodynamics. This is particularly challenging since all QED textbooks state that such a splitting cannot be done for a photon (and a fortiori for a gluon) in a gauge-invariant way, yet experimentalists around the world are engaged in measuring what they believe is the gluon spin! This question has been a subject of intense debate and controversy, ever since, in 2008, it was claimed that such a gauge-invariant split was, in fact, possible. We explain in what sense this claim is true and how it turns out that one of the main problems is that such a decomposition is not unique and therefore raises the question of what is the most natural or physical choice. The essential requirement of measurability does not solve the ambiguities and leads us to the conclusion that the choice of a particular decomposition is essentially a matter of taste and convenience. In this review, we provide a pedagogical introduction to the question of angular momentum decomposition in a gauge theory, present the main relevant decompositions and discuss in detail several aspects of the controversies regarding the question of gauge invariance, frame dependence, uniqueness and measurability. We stress the physical implications of the recent developments and collect into a separate section all the sum rules and relations which we think experimentally relevant. We hope that such a review will make the matter amenable to a broader community and will help to clarify the present situation.     

The angular momentum controversy: What’s it all about and does it matter?

A controversy has arisen as to how to define quark and gluon angular momentum, important in understanding the internal structure of the nucleon. For a review of the controversy, see [1]. I survey some of the ideas put forward and try to assess their physical implications.     

Entanglement Sudden Death in Quantum Optics： What is it and why does it happen？

It is well known in quantum optics that fluctuations and dissipation inevitably intervene in the dynamics of open quantum systems. Density matrix elements may all decay exponentially and smoothly but we show that two-party entanglement, a valuable quantum coherence, may nevertheless abruptly decrease to zero in a finite time. This is Entanglement Sudden Death. In this talk we show how entanglement sudden death occurs under either phase or amplitude noise, either quantum or classical in origin. Moreover, we show that when two or more noises are active at the same time, the effects of the combined noises is even more unexpected.     

Underwater wireless optical communication:why,what, and how? [Invited]

Foreseeing the proliferation of underwater vehicles and sensors, underwater wireless optical communication(UWOC) is a key enabler for ocean exploration, with strong competitiveness in short-range bandwidth-intensive applications. We provide a tutorial on the basic concepts and essential features of UWOC, as well as an overview of work being conducted in this field. Research challenges, arising from the characteristics of underwater channels, and possible roadmaps are discussed in detail. This review is expected to be of great use for the link designers of this field.     

Nanotechnology,voluntary oversight,and corporate social performance: does company size matter?

In this article, we examine voluntary oversight programs for nanotechnology in the context of corporate social performance (CSP) in order to better understand the drivers, barriers, and forms of company participation in such programs. At the theoretical level, we use the management framework of CSP to understand the voluntary behavior of companies. At the empirical level, we investigate nanotech industry participation in the Environmental Protection Agency’s Nanoscale Materials Stewardship Program (NMSP) as an example of CSP, in order to examine the effects of company characteristics on CSP outcomes. The analysis demonstrates that, on the average, older and larger companies for which nanotech is one of the many business activities demonstrate greater CSP as judged by company actions, declarations, and self-evaluations. Such companies tended to submit more of the requested information to the NMSP, including specific information about health and safety, and to claim fewer of the submitted items as confidential business information. They were also more likely to have on-line statements of generic and nano-specific corporate social responsibility principles, policies, and achievements. The article suggests a need to encourage smaller and younger companies to participate in voluntary oversight programs for nanotechnology and presents options for better design of these programs.     

Field-induced self-assembly: does size matter?

ABSTRACT

Simulated external electric fields are applied to polarisable species containing either a monodisperse of bidisperse distribution of polarisabilities. The magnitude of the external field and the polarisabilities are systematically varied. The application of an external field (of sufficient magnitude) is found to induce chain formation (as expected). The monodisperse systems are found to ‘self-assemble’ with larger induced dipole moments effectively clustering in chains as a result of significant dipole-induced dipole effects. The distribution of the chain lengths is characterised as a function of the applied field and the atom polarisability. For the bidisperse systems, the external field induces chain formation and a partial segregation, in which the more polarisable species preferentially form chains. The chain lengths are again determined as a function of field strength and the atom polarisabilities. Scaling behaviour is analysed.     

What is 'unfreezable water', how unfreezable is it,and how much is there?

Water that remains unfrozen at temperatures below the equilibrium bulk freezing temperature, in the presence of ice, is sometimes called unfreezable or bound. This paper analyses the phenomenon in terms of quantitative measurements of the hydration interaction among membranes or macromolecules at freezing temperatures. These results are related to analogous measurements in which osmotic stress or mechanical compression is used to equilibrate water of hydration with a bulk phase. The analysis provides formulas to estimate, at a given sub-freezing temperature, the amount of unfrozen water due to equilibrium hydration effects. Even at tens of degrees below freezing, this hydration effect alone can explain an unfrozen water volume that considerably exceeds that of a single 'hydration shell' surrounding the hydrophilic surfaces. The formulas provided give a lower bound to the amount of unfrozen water for two reasons. First, the well-known freezing point depression due to small solutes is, to zeroth order, independent of the membrane or macromolecular hydration effect. Further, the unfrozen solution found between membranes or macromolecules at freezing temperatures has high viscosity and small dimensions. This means that dehydration of such systems, especially at freezing temperatures, takes so long that equilibrium is rarely achieved over normal experimental time scales. So, in many cases, the amount of unfrozen water exceeds that expected at equilibrium, which in turn usually exceeds that calculated for a single hydration shell.     

What is modified gravity and how to differentiate it from particle dark matter?

An obvious criterion to classify theories of modified gravity is to identify their gravitational degrees of freedom and their coupling to the metric and the matter sector. Using this simple idea, we show that any theory which depends on the curvature invariants is equivalent to general relativity in the presence of new fields that are gravitationally coupled to the energy-momentum tensor. We show that they can be shifted into a new energy-momentum tensor. There is no a priori reason to identify these new fields as gravitational degrees of freedom or matter fields. This leads to an equivalence between dark matter particles gravitationally coupled to the standard model fields and modified gravity theories designed to account for the dark matter phenomenon. Due to this ambiguity, it is impossible to differentiate experimentally between these theories and any attempt of doing so should be classified as a mere interpretation of the same phenomenon.     

Desktop supercomputer: what can it do?

The paper addresses the issues of solving complex problems that require using supercomputers or multiprocessor clusters available for most researchers nowadays. Efficient distribution of high performance computing resources according to actual application needs has been a major research topic since high-performance computing (HPC) technologies became widely introduced. At the same time, comfortable and transparent access to these resources was a key user requirement. In this paper we discuss approaches to build a virtual private supercomputer available at user’s desktop: a virtual computing environment tailored specifically for a target user with a particular target application. We describe and evaluate possibilities to create the virtual supercomputer based on light-weight virtualization technologies, and analyze the efficiency of our approach compared to traditional methods of HPC resource management.     

MeV dark matter: has it been detected?

We discuss the possibility that the recent detection of 511 keV gamma rays from the galactic bulge, as observed by INTEGRAL, is a consequence of low mass (1-100 MeV) particle dark matter annihilations. We discuss the type of halo profile favored by the observations as well as the size of the annihilation cross section needed to account for the signal. We find that such a scenario is consistent with the observed dark matter relic density and other constraints from astrophysics and particle physics.     

Identification and discrimination of rise time: is it categorical or noncategorical?

Previous studies have reported that rise time of sawtooth waveforms may be discriminated in either a categorical-like manner under some experimental conditions or according to Weber's law under other conditions. In the present experiments, rise time discrimination was examined with two experimental procedures: the traditional labeling and ABX tasks used in speech perception studies and an adaptive tracking procedure used in psychophysical studies. Rise time varied from 0 to 80 ms in 10-ms intervals for sawtooth signals of 1-s duration. Discrimination functions for subjects who simply discriminated the signals on any basis whatsoever as well as functions for subjects who practiced labeling the endpoint stimuli as " pluck " and "bow" before ABX discrimination were not categorical in the ABX task. In the adaptive tracking procedure, the Weber fraction obtained from the jnds of rise time was found to be a constant above 20-ms rise time. The results from the two discrimination paradigms were then compared by predicting a jnd for rise time from the ABX discrimination data by reference to the underlying psychometric function. Using this method of analysis, discrimination results from previous studies were shown to be quite similar to the discrimination results observed in this study. Taken together the results demonstrate clearly that rise time discrimination of sawtooth signals follows predictions derived from Weber's law.     

If "discrete breathers" is the answer,what is the question?

Intense work on discrete breathers or intrinsic localized modes in recent years has revealed a wealth of new properties of classical energy localization. Relaxation and mobility in particular may be two of the critical links with biomolecular processes. We review some of the basic discrete breather properties that we think are pertinent to biomolecules and make conjectures as to their possible biological utility.     

Results from PAMELA,ATIC and FERMI: Pulsars or dark matter?

It is well known that dark matter dominates the dynamics of galaxies and clusters of galaxies. Its constituents remain a mystery despite an assiduous search for them over the past three decades. Recent results from the satellite-based PAMELA experiment show an excess in the positron fraction at energies between 10 and 100 GeV in the secondary cosmic ray spectrum. Other experiments, namely ATIC, HESS and FERMI, show an excess in the total electron (e ⁺ + e ⁻) spectrum for energies greater than 100 GeV. These excesses in the positron fraction as well as the electron spectrum can arise in local astrophysical processes like pulsars, or can be attributed to the annihilation of the dark matter particles. The latter possibility gives clues to the possible candidates for the dark matter in galaxies and other astrophysical systems. In this article, we give a report of these exciting developments.     

Surface pressure in clusters and small particles—is it real?

Using the methods of statistical mechanics and applying the conditions of thermal equilibrium for an ensemble of interacting molecules, it is proved that there is no excess pressure, nor internal and surface stresses, in clusters and small particles that are not subjected to the action of external forces. With this premise taken into account the thermodynamics of spherical and faceted small particles is developed. In a particle-vapour system surrounded by a rigid impervious shell, Kelvin's and Thomson's formulae and Wulff's rule are derived. For a particle-melt system at a constant external pressure it is expected that the melting points of a particle and a bulk solid should be equal. It is noted that, if a particle is not subjected to the action of external fields or bodies, its molecules occupy their natural equilibrium positions, and it is from them that deformations and internal stresses should be counted off. These equilibrium positions differ from those occupied by the same molecules in a bulk solid, which is what usually gives rise to the illusions of the stressed state of a small particle and its deformation caused by the “uncompensated” surface forces.