Studying reactive processes with classical dynamics: rebinding dynamics in MbNO

A new surface-crossing algorithm suitable for describing bond-breaking and bond-forming processes in molecular dynamics simulations is presented. The method is formulated for two intersecting potential energy manifolds which dissociate to different adiabatic states. During simulations, crossings are detected by monitoring an energy criterion. If fulfilled, the two manifolds are mixed over a finite number of time steps, after which the system is propagated on the second adiabat and the crossing is carried out with probability one. The algorithm is extensively tested (almost 0.5 mu s of total simulation time) for the rebinding of NO to myoglobin. The unbound surface ((FeNO)-N-...) is represented using a standard force field, whereas the bound surface (Fe-NO) is described by an ab initio potential energy surface. The rebinding is found to be nonexponential in time, in agreement with experimental studies, and can be described using two time constants. Depending on the asymptotic energy separation between the manifolds, the short rebinding timescale is between 1 and 9 ps, whereas the longer timescale is about an order of magnitude larger. NO molecules which do not rebind within 1 ns are typically found in the Xenon-4 pocket, indicating the high affinity of NO to this region in the protein.

Calculation of converged rovibrational energies and partition function for methane using vibrational-rotational configuration interaction

The rovibration partition function of CH4 was calculated in the temperature range of 100-1000 K using well-converged energy levels that were calculated by vibrational-rotational configuration interaction using the Watson Hamiltonian for total angular momenta J=0-50 and the MULTIMODE computer program. The configuration state functions are products of ground-state occupied and virtual modals obtained using the vibrational self-consistent field method. The Gilbert and Jordan potential energy surface was used for the calculations. The resulting partition function was used to test the harmonic oscillator approximation and the separable-rotation approximation. The harmonic oscillator, rigid-rotator approximation is in error by a factor of 2.3 at 300 K, but we also propose a separable-rotation approximation that is accurate within 2% from 100 to 1000 K. (C) 2004 American Institute of Physics.

Dynamics of convectively driven banded jets in the laboratory

The banded organization of clouds and zonal winds in the atmospheres of the outer planets has long fascinated observers. Several recent studies in the theory and idealized modeling of geostrophic turbulence have suggested possible explanations for the emergence of such organized patterns, typically involving highly anisotropic exchanges of kinetic energy and vorticity within the dissipationless inertial ranges of turbulent flows dominated (at least at large scales) by ensembles of propagating Rossby waves. The results from an attempt to reproduce such conditions in the laboratory are presented here. Achievement of a distinct inertial range turns out to require an experiment on the largest feasible scale. Deep, rotating convection on small horizontal scales was induced by gently and continuously spraying dense, salty water onto the free surface of the 13-m-diameter cylindrical tank on the Coriolis platform in Grenoble, France. A “planetary vorticity gradient” or “β effect” was obtained by use of a conically sloping bottom and the whole tank rotated at angular speeds up to 0.15 rad s−1. Over a period of several hours, a highly barotropic, zonally banded large-scale flow pattern was seen to emerge with up to 5–6 narrow, alternating, zonally aligned jets across the tank, indicating the development of an anisotropic field of geostrophic turbulence. Using particle image velocimetry (PIV) techniques, zonal jets are shown to have arisen from nonlinear interactions between barotropic eddies on a scale comparable to either a Rhines or “frictional” wavelength, which scales roughly as (β/Urms)−1/2. This resulted in an anisotropic kinetic energy spectrum with a significantly steeper slope with wavenumber k for the zonal flow than for the nonzonal eddies, which largely follows the classical Kolmogorov k−5/3 inertial range. Potential vorticity fields show evidence of Rossby wave breaking and the presence of a “hyperstaircase” with radius, indicating instantaneous flows that are supercritical with respect to the Rayleigh–Kuo instability criterion and in a state of “barotropic adjustment.” The implications of these results are discussed in light of zonal jets observed in planetary atmospheres and, most recently, in the terrestrial oceans.

Synthesis of a catechol-based poly(ether ether ketone) ("o-PEEK") by classical step-growth polymerization and by entropically driven ring-opening polymerization of macrocyclic oligomers

An amorphous, catechol-based analogue of PEEK ("o-PEEK") has been prepared by a classical step-growth polymerization reaction between catechol and 4,4'-difluorobenzophenone and shown to be readily soluble in a range of organic solvents. Copolymers with p-PEEK have been investigated, including an amorphous 50: 50 composition and a semicrystalline though still organic-soluble material comprising 70% p-PEEK. o-PEEK has also been obtained by entropy-driven ring-opening polymerization of the macrocyclic oligomers (MCO's) formed by cyclo-condensation of catechol with 4,4'-difluorobenzophenone under pseudo-high-dilution conditions. The principal products of this latter reaction were the cyclic dimer 3a (20 wt %), cyclic trimer 3b (16%) cyclic tetramer 3c (14%), cyclic pentamer 3d (13%) and cyclic hexamer 3e (12%). Macrocycles 3a-c were isolated as pure compounds by gradient column chromatography, and the structures of the cyclic dimer 3a and cyclic tetramer 3c were analyzed by single-crystal X-ray diffraction. A mixture of MCO's, 3, of similar composition, was obtained by cyclodepolymerization of high molar mass o-PEEK in dilute soluion.

The frequency and dynamics of stratospheric sudden warmings in the 21st century

Changes to stratospheric sudden warmings (SSWs) over the coming century, as predicted by the Geophysical Fluid Dynamics Laboratory (GFDL) chemistry climate model [Atmospheric Model With Transport and Chemistry (AMTRAC)], are investigated in detail. Two sets of integrations, each a three-member ensemble, are analyzed. The first set is driven with observed climate forcings between 1960 and 2004; the second is driven with climate forcings from a coupled model run, including trace gas concentrations representing a midrange estimate of future anthropogenic emissions between 1990 and 2099. A small positive trend in the frequency of SSWs is found. This trend, amounting to 1 event/decade over a century, is statistically significant at the 90% confidence level and is consistent over the two sets of model integrations. Comparison of the model SSW climatology between the late 20th and 21st centuries shows that the increase is largest toward the end of the winter season. In contrast, the dynamical properties are not significantly altered in the coming century, despite the increase in SSW frequency. Owing to the intrinsic complexity of our model, the direct cause of the predicted trend in SSW frequency remains an open question.

The two-dimensional anharmonic oscillator I: vibration-rotation constants of fulminic acid, HCNO

The lowest-wavenumber vibration of HCNO and DCNO, ν5, is known to involve a largeamplitude low-frequency anharmonic bending of the CH bond against the CNO frame. In this paper the anomalous vibrational dependence of the observed rotational constants B(v5, l5), and of the observed l-doubling interactions, is interpreted according to a simple effective vibration-rotation Hamiltonian in which the appropriate vibrational operators are averaged in an anharmonic potential surface over the normal coordinates (Q5x, Q5y). All of the data on both isotopes are interpreted according to a single potential surface having a minimum energy at a slightly bent configuration of the HCN angle ( 170°) with a maximum at the linear configuration about 2 cm−1 higher. The other coefficients in the Hamiltonian are also interpreted in terms of the structure and the harmonic and anharmonic force fields; the substitution structure at the “hypothetical linear configuration” determined in this way gives a CH bond length of 1.060 Å, in contrast to the value 1.027 Å determined from the ground-state rotational constants. We also discuss the difficulties in rationalizing our effective Hamiltonian in terms of more fundamental theory, as well as the success and limitations of its use in practice.

Wave-driven wind jets in the marine atmospheric boundary layer

The interaction between ocean surface waves and the overlying wind leads to a transfer of momentum across the air–sea interface. Atmospheric and oceanic models typically allow for momentum transfer to be directed only downward, from the atmosphere to the ocean. Recent observations have suggested that momentum can also be transferred upward when long wavelength waves, characteristic of remotely generated swell, propagate faster than the wind speed. The effect of upward momentum transfer on the marine atmospheric boundary layer is investigated here using idealized models that solve the momentum budget above the ocean surface. A variant of the classical Ekman model that accounts for the wave-induced stress demonstrates that, although the momentum flux due to the waves penetrates only a small fraction of the depth of the boundary layer, the wind profile is profoundly changed through its whole depth. When the upward momentum transfer from surface waves sufficiently exceeds the downward turbulent momentum flux, then the near-surface wind accelerates, resulting in a low-level wave-driven wind jet. This increases the Coriolis force in the boundary layer, and so the wind turns in the opposite direction to the classical Ekman layer. Calculations of the wave-induced stress due to a wave spectrum representative of fast-moving swell demonstrate upward momentum transfer that is dominated by contributions from waves in the vicinity of the peak in the swell spectrum. This is in contrast to wind-driven waves whose wave-induced stress is dominated by very short wavelength waves. Hence the role of swell can be characterized by the inverse wave age based on the wave phase speed corresponding to the peak in the spectrum. For a spectrum of waves, the total momentum flux is found to reverse sign and become upward, from waves to wind, when the inverse wave age drops below the range 0.15–0.2, which agrees reasonably well with previously published oceanic observations.

Molecular dynamics simulation of interactions between a sodium dodecyl sulfate micelle and a poly(ethylene oxide) polymer

We have performed atomistic molecular dynamics simulations of an anionic sodium dodecyl sulfate (SDS) micelle and a nonionic poly(ethylene oxide) (PEO) polymer in aqueous solution. The micelle consisted of 60 surfactant molecules, and the polymer chain lengths varied from 20 to 40 monomers. The force field parameters for PEO were adjusted by using 1,2-dimethoxymethane (DME) as a model compound and matching its hydration enthalpy and conformational behavior to experiment. Excellent agreement with previous experimental and simulation work was obtained through these modifications. The simulated scaling behavior of the PEO radius of gyration was also in close agreement with experimental results. The SDS-PEO simulations show that the polymer resides on the micelle surface and at the hydrocarbon-water interface, leading to a selective reduction in the hydrophobic contribution to the solvent-accessible surface area of the micelle. The association is mainly driven by hydrophobic interactions between the polymer and surfactant tails, while the interaction between the polymer and sulfate headgroups on the micelle surface is weak. The 40-monomer chain is mostly wrapped around the micelle, and nearly 90% of the monomers are adsorbed at low PEO concentration. Simulations were also performed with multiple 20-monomer chains, and gradual addition of polymer indicates that about 120 monomers are required to saturate the micelle surface. The stoichiometry of the resulting complex is in close agreement with experimental results, and the commonly accepted "beaded necklace" structure of the SDS-PEO complex is recovered by our simulations.

Suspended and bed load sediment transport dynamics in two lowland UK streams—storm integrated monitoring

A great deal of work recently has focused on suspended and bedload sediment transport, driven primarily by interest in contaminant transfer. However, uncertainties regarding the role of storm events, macrophyte beds and interactions between the two phases of sediment still exist. This paper compares two study sites within the same catchment whose geology varies significantly. The differences in hydrology, suspended sediment (SS) transport and bed load transport that this causes are examined. In addition, a method to predict the mobilization of different size fractions of sediment during given flows is investigated using critical entrainment thresholds.

Dynamics of the lower stratospheric circulation response to ENSO

A robust feature of the observed response to El Nin˜o–Southern Oscillation (ENSO) is an altered circulation in the lower stratosphere. When sea surface temperatures (SSTs) in the tropical Pacific are warmer there is enhanced upwelling and cooling in the tropical lower stratosphere and downwelling and warming in the midlatitudes, while the opposite is true of cooler SSTs. The midlatitude lower stratospheric response to ENSO is larger in the Southern Hemisphere (SH) than in the Northern Hemisphere (NH). In this study the dynamical version of the Canadian Middle Atmosphere Model (CMAM) is used to simulate 25 realizations of the atmospheric response to the 1982/83 El Nin˜o and the 1973/74 La Nin˜ a. This version ofCMAMis a comprehensive high-top general circulation model that does not include interactive chemistry. The observed lower stratospheric response to ENSO is well reproduced by the simulations, allowing them to be used to investigate the mechanisms involved. Both the observed and simulated responses maximize in December–March and so this study focuses on understanding the mechanisms involved in that season. The response in tropical upwelling is predominantly driven by anomalous transient synoptic-scale wave drag in the SH subtropical lower stratosphere, which is also responsible for the compensating SH midlatitude response. This altered wave drag stems from an altered upward flux of wave activity from the troposphere into the lower stratosphere between 208 and 408S. The altered flux of wave activity can be divided into two distinct components. In the Pacific, the acceleration of the zonal wind in the subtropics from the warmer tropical SSTs results in a region between the midlatitude and subtropical jets where there is an enhanced source of low phase speed eddies. At other longitudes, an equatorward shift of the midlatitude jet from the extratropical tropospheric response to El Nin˜o results in an enhanced source of waves of higher phase speeds in the subtropics. The altered resolved wave drag is only apparent in the SH and the difference between the two hemispheres can be related to the difference in the climatological jet structures in this season and the projection of the wind anomalies associated with ENSO onto those structures.

Zonal-mean dynamics of extended recoveries from stratospheric sudden warmings

The recovery of the Arctic polar vortex following stratospheric sudden warmings is found to take upward of 3 months in a particular subset of cases, termed here polar-night jet oscillation (PJO) events. The anomalous zonal-mean circulation above the pole during this recovery is characterized by a persistently warm lower stratosphere, and above this a cold midstratosphere and anomalously high stratopause, which descends as the event unfolds. Composites of these events in the Canadian Middle Atmosphere Model show the persistence of the lower-stratospheric anomaly is a result of strongly suppressed wave driving and weak radiative cooling at these heights. The upper-stratospheric and lower-mesospheric anomalies are driven immediately following the warming by anomalous planetary-scale eddies, following which, anomalous parameterized nonorographic and orographic gravity waves play an important role. These details are found to be robust for PJO events (as opposed to sudden warmings in general) in that many details of individual PJO events match the composite mean. Azonal-mean quasigeostrophic model on the sphere is shown to reproduce the response to the thermal and mechanical forcings produced during a PJO event. The former is well approximated by Newtonian cooling. The response can thus be considered as a transient approach to the steady-state, downward control limit. In this context, the time scale of the lower-stratospheric anomaly is determined by the transient, radiative response to the extended absence of wave driving. The extent to which the dynamics of the wave-driven descent of the stratopause can be considered analogous to the descending phases of the quasi-biennial oscillation (QBO) is also discussed.

Energetics of a symmetric circulation including momentum constraints

A theory of available potential energy (APE) for symmetric circulations, which includes momentum constraints, is presented. The theory is a generalization of the classical theory of APE, which includes only thermal constraints on the circulation. Physically, centrifugal potential energy is included along with gravitational potential energy. The generalization relies on the Hamiltonian structure of the conservative dynamics, although (as with classical APE) it still defines the energetics in a nonconservative framework. It follows that the theory is exact at finite amplitude, has a local form, and can be applied to a variety of fluid models. It is applied here to the f -plane Boussinesq equations. It is shown that, by including momentum constraints, the APE of a symmetrically stable flow is zero, while the energetics of a mechanically driven symmetric circulation properly reflect its causality.

Hamiltonian geophysical fluid dynamics

Hamiltonian dynamics describes the evolution of conservative physical systems. Originally developed as a generalization of Newtonian mechanics, describing gravitationally driven motion from the simple pendulum to celestial mechanics, it also applies to such diverse areas of physics as quantum mechanics, quantum field theory, statistical mechanics, electromagnetism, and optics – in short, to any physical system for which dissipation is negligible. Dynamical meteorology consists of the fundamental laws of physics, including Newton’s second law. For many purposes, diabatic and viscous processes can be neglected and the equations are then conservative. (For example, in idealized modeling studies, dissipation is often only present for numerical reasons and is kept as small as possible.) In such cases dynamical meteorology obeys Hamiltonian dynamics. Even when nonconservative processes are not negligible, it often turns out that separate analysis of the conservative dynamics, which fully describes the nonlinear interactions, is essential for an understanding of the complete system, and the Hamiltonian description can play a useful role in this respect. Energy budgets and momentum transfer by waves are but two examples.

Free gravity waves and balanced dynamics

It is shown how a renormalization technique, which is a variant of classical Krylov–Bogolyubov–Mitropol’skii averaging, can be used to obtain slow evolution equations for the vortical and inertia–gravity wave components of the dynamics in a rotating flow. The evolution equations for each component are obtained to second order in the Rossby number, and the nature of the coupling between the two is analyzed carefully. It is also shown how classical balance models such as quasigeostrophic dynamics and its second-order extension appear naturally as a special case of this renormalized system, thereby providing a rigorous basis for the slaving approach where only the fast variables are expanded. It is well known that these balance models correspond to a hypothetical slow manifold of the parent system; the method herein allows the determination of the dynamics in the neighborhood of such solutions. As a concrete illustration, a simple weak-wave model is used, although the method readily applies to more complex rotating fluid models such as the shallow-water, Boussinesq, primitive, and 3D Euler equations.