A method of ‘‘natural population analysis’’ has been developed to calculate atomic charges and orbital populations of molecular wave functions in general atomic orbital basis sets. The natural analysis is an alternative to conventional Mulliken population analysis, and seems to exhibit improved numerical stability and to better describe the electron distribution in compounds of high ionic character, such as those containing metal atoms. We calculated ab initio SCF‐MO wave functions for compounds of type CH3X and LiX (X=F, OH, NH2, CH3, BH2, BeH, Li, H) in a variety of basis sets to illustrate the generality of the method, and to compare the natural populations with results of Mulliken analysis, density integration, and empirical measures of ionic character. Natural populations are found to give a satisfactory description of these molecules, providing a unified treatment of covalent and extreme ionic limits at modest computational cost.

Natural population analysis

When a spilled drop of coffee dries on a solid surface, it leaves a dense, ring-like deposit along the perimeter (Fig 1a) The coffee—initially dispersed over the entire drop—becomes concentrated into a tiny fraction of it Such ring deposits are common wherever drops containing dispersed solids evaporate on a surface, and they influence processes such as printing, washing and coating1,2,3,4,5 Ring deposits also provide a potential means to write or deposit a fine pattern onto a surface Here we ascribe the characteristic pattern of the deposition to a form of capillary flow in which pinning of the contact line of the drying drop ensures that liquid evaporating from the edge is replenished by liquid from the interior The resulting outward flow can carry virtually all the dispersed material to the edge This mechanism predicts a distinctive power-law growth of the ring mass with time—a law independent of the particular substrate, carrier fluid or deposited solids We have verified this law by microscopic observations of colloidal fluids

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Capillary flow as the cause of ring stains from dried liquid drops

Optical tweezers use the forces exerted by a strongly focused beam of light to trap and move objects ranging in size from tens of nanometres to tens of micrometres. Since their introduction in 1986, the optical tweezer has become an important tool for research in the fields of biology, physical chemistry and soft condensed matter physics. Recent advances promise to take optical tweezers out of the laboratory and into the mainstream of manufacturing and diagnostics; they may even become consumer products. The next generation of single-beam optical traps offers revolutionary new opportunities for fundamental and applied research.

http://physics.nyu.edu/grierlab/nreview2c/nreview2c.pdf

A revolution in optical manipulation

Microfabricated integrated circuits revolutionized computation by vastly reducing the space, labor, and time required for calculations. Microfluidic systems hold similar promise for the large-scale automation of chemistry and biology, suggesting the possibility of numerous experiments performed rapidly and in parallel, while consuming little reagent. While it is too early to tell whether such a vision will be realized, significant progress has been achieved, and various applications of significant scientific and practical interest have been developed. Here a review of the physics of small volumes (nanoliters) of fluids is presented, as parametrized by a series of dimensionless numbers expressing the relative importance of various physical phenomena. Specifically, this review explores the Reynolds number Re, addressing inertial effects; the Peclet number Pe, which concerns convective and diffusive transport; the capillary number Ca expressing the importance of interfacial tension; the Deborah, Weissenberg, and elasticity numbers De, Wi, and El, describing elastic effects due to deformable microstructural elements like polymers; the Grashof and Rayleigh numbers Gr and Ra, describing density-driven flows; and the Knudsen number, describing the importance of noncontinuum molecular effects. Furthermore, the long-range nature of viscous flows and the small device dimensions inherent in microfluidics mean that the influence of boundaries is typically significant. A variety of strategies have been developed to manipulate fluids by exploiting boundary effects; among these are electrokinetic effects, acoustic streaming, and fluid-structure interactions. The goal is to describe the physics behind the rich variety of fluid phenomena occurring on the nanoliter scale using simple scaling arguments, with the hopes of developing an intuitive sense for this occasionally counterintuitive world.

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Microfluidics: Fluid physics at the nanoliter scale

Stochastic thermodynamics as reviewed here systematically provides a framework for extending the notions of classical thermodynamics such as work, heat and entropy production to the level of individual trajectories of well-defined non-equilibrium ensembles. It applies whenever a non-equilibrium process is still coupled to one (or several) heat bath(s) of constant temperature. Paradigmatic systems are single colloidal particles in time-dependent laser traps, polymers in external flow, enzymes and molecular motors in single molecule assays, small biochemical networks and thermoelectric devices involving single electron transport. For such systems, a first-law like energy balance can be identified along fluctuating trajectories. For a basic Markovian dynamics implemented either on the continuum level with Langevin equations or on a discrete set of states as a master equation, thermodynamic consistency imposes a local-detailed balance constraint on noise and rates, respectively. Various integral and detailed fluctuation theorems, which are derived here in a unifying approach from one master theorem, constrain the probability distributions for work, heat and entropy production depending on the nature of the system and the choice of non-equilibrium conditions. For non-equilibrium steady states, particularly strong results hold like a generalized fluctuation–dissipation theorem involving entropy production. Ramifications and applications of these concepts include optimal driving between specified states in finite time, the role of measurement-based feedback processes and the relation between dissipation and irreversibility. Efficiency and, in particular, efficiency at maximum power can be discussed systematically beyond the linear response regime for two classes of molecular machines, isothermal ones such as molecular motors, and heat engines such as thermoelectric devices, using a common framework based on a cycle decomposition of entropy production. (Some figures may appear in colour only in the online journal) This article was invited by Erwin Frey.

/pdf/stochastic-thermodynamics-fluctuation-theorems-and-molecular-2epwyvmpf0.pdf

Stochastic thermodynamics, fluctuation theorems and molecular machines

http://crocker.seas.upenn.edu/CrockerGrier1996b.pdf

Methods of Digital Video Microscopy for Colloidal Studies

https://physics.nyu.edu/grierlab/dynamic5b/dynamic5b.pdf

Dynamic holographic optical tweezers

We present a method of calculating the electric charge density of glass and silica surfaces in contact with aqueous electrolytes for two cases of practical relevance that are not amenable to standard techniques: surfaces of low specific area at low ionic strength and surfaces interacting strongly with a second anionic surface.

https://physics.nyu.edu/grierlab/charge6c/charge6c.pdf

The charge of glass and silica surfaces

https://arxiv.org/pdf/cond-mat/0105149.pdf

David G. Grier

Papers

A revolution in optical manipulation

Methods of Digital Video Microscopy for Colloidal Studies

Dynamic holographic optical tweezers

The charge of glass and silica surfaces

The Charge of Glass and Silica Surfaces