Rovibrational energy levels for the electronic ground state of A1OH

The vibrational-rotational energy levels of aluminum monohydroxide in its electronic ground state, (A) over tilde (1)A' AlOH, have been predicted using the variational method. The potential energy surface of the (X) over tilde (1)A' ground state of AlOH was determined employing the ab initio coupled cluster method with single, double, and perturbative triple excitations [CCSD(T)] and the correlation-consistent polarized valence quadruple zeta (cc-pVQZ) basis set. Low-lying J= 0 and J= 1 vibrational levels are reported. These are analyzed in terms of the quasilinearity of the molecule. Coriolis effects are shown to be significant. We hope that our predictions will be of value in the future when assigning rovibrational transitions in spectroscopic studies. (c) 2006 Elsevier B.V. All rights reserved.

Theoretical calculation of absorption intensities of C2H and C2D

The theory of dipole-allowed absorption intensities in triatomic molecules is presented for systems with three close-lying electronic states of doublet multiplicity. Its derivation is within the framework of a recently developed variational method [CARTER, S., HANDY, N. C., PUZZARINI, C., TARRONI, R., and PALMIERI, P., 2000, Molec. Phys., 98,1967]. The method has been applied to the calculation of the infrared absorption spectrum of the C2H radical and its deuterated isotopomer for energies up to 10000 cm(-1) above the ground state, using highly accurate ab initio diabatic potential energy and dipole moment surfaces. The calculated spectra agree very well with those recorded experimentally in a neon matrix [FORNEY, D., JACOX, M. E., and THOMPSON, W. E., 1995, J. molee. Spectrosc., 170, 178] and assignments in the high energy region of the IR spectra are proposed for the first time.

Ab initio prediction of the infrared absorption spectrum of the C2Br radical

The first three electronic states (1(2)A', 2(2)A', 1(2)A '') of the C2Br radical, correlating at linear geometries with (2)Sigma(+) and (2)Pi states, have been studied ab initio, using Multi Reference Configuration Interaction techniques. The electronic ground state is found to have a bent equilibrium geometry, R-CC = 1.2621 angstrom, R-CBr = 1.7967 angstrom, < CCBr 156.1 degrees, with a very low barrier to linearity. Similarly to the valence isoelectronic radicals C2F and C2Cl, this anomalous behaviour is attributed to a strong three-state non-adiabatic electronic interaction. The Sigma, Pi(1/2), Pi(3/2) vibronic energy levels and their absolute infrared absorption intensities at a temperature of 5K have been calculated for the (CCBr)-C-12-C-12-Br-79 isotopomer, to an upper limit of 2000 cm(-1), using ab initio diabatic potential energy and dipole moment surfaces and a recently developed variational method.

On the available energy of an axisymmetric vortex

A theory of available energy for axisymmetric circulations is presented. The theory is a generalization of the classical theory of available potential energy, in that it accounts for both thermal and angular momentum constraints on the circulation. The generalization relies on the Hamiltonian structure of the (conservative) dynamics, is exact at finite amplitude, and has a local form. Application of the theory is presented for the case of an axisymmetric vortex on an f -plane in the context of the Boussinesq equations.

Linking urban water balance and energy balance models to analyse urban design options

Using a water balance modelling framework, this paper analyses the effects of urban design on the water balance, with a focus on evapotranspiration and storm water. First, two quite different urban water balance models are compared: Aquacycle which has been calibrated for a suburban catchment in Canberra, Australia, and the single-source urban evapotranspiration-interception scheme (SUES), an energy-based approach with a biophysically advanced representation of interception and evapotranspiration. A fair agreement between the two modelled estimates of evapotranspiration was significantly improved by allowing the vegetation cover (leaf area index, LAI) to vary seasonally, demonstrating the potential of SUES to quantify the links between water sensitive urban design and microclimates and the advantage of comparing the two modelling approaches. The comparison also revealed where improvements to SUES are needed, chiefly through improved estimates of vegetation cover dynamics as input to SUES, and more rigorous parameterization of the surface resistance equations using local-scale suburban flux measurements. Second, Aquacycle is used to identify the impact of an array of water sensitive urban design features on the water balance terms. This analysis confirms the potential to passively control urban microclimate by suburban design features that maximize evapotranspiration, such as vegetated roofs. The subsequent effects on daily maximum air temperatures are estimated using an atmospheric boundary layer budget. Potential energy savings of about 2% in summer cooling are estimated from this analysis. This is a clear ‘return on investment’ of using water to maintain urban greenspace, whether as parks distributed throughout an urban area or individual gardens or vegetated roofs.

On the validity of single-parcel energetics to assess the importance of internal energy and compressibility effects in stratified fluids

It is often assumed on the basis of single-parcel energetics that compressible effects and conversions with internal energy are negligible whenever typical displacements of fluid parcels are small relative to the scale height of the fluid (defined as the ratio of the squared speed of sound over gravitational acceleration). This paper shows that the above approach is flawed, however, and that a correct assessment of compressible effects and internal energy conversions requires considering the energetics of at least two parcels, or more generally, of mass conserving parcel re-arrangements. As a consequence, it is shown that it is the adiabatic lapse rate and its derivative with respect to pressure, rather than the scale height, which controls the relative importance of compressible effects and internal energy conversions when considering the global energy budget of a stratied fluid. Only when mass conservation is properly accounted for is it possible to explain why available internal energy can account for up to 40 percent of the total available potential energy in the oceans. This is considerably larger than the prediction of single-parcel energetics, according to which this number should be no more than about 2 percent.

Energy performance ratings and house prices in Wales: an empirical study

This paper investigates the price effect of EPC ratings on the residential dwelling prices in Wales. It examines the capitalisation of energy efficiency ratings into house prices using two approaches. The first adopts a cross-sectional framework to investigate the effect of EPC band (and EPC rating) on a large sample of dwelling transactions. The second approach is based on a repeat-sales methodology to examine the impact of EPC band and rating on house price appreciation. The results show that, controlling for other price influencing dwelling characteristics, EPC band does affect house prices. This observed influence of EPC on price may not be a result of energy performance alone; the effect may be due to non-energy related benefits associated with certain types, specifications and ages of dwellings or there may be unobserved quality differences unrelated to energy performance such as better quality fittings and materials. An analysis of the private rental segment reveals that, in contrast to the general market, low-EPC rated properties were not traded at a significant discount, suggesting different implicit prices of potential energy savings for landlords and owner-occupiers.

Energy performance ratings and house prices in Wales: an empirical study

This paper investigates the effect of Energy Performance Certificate (EPC) ratings on residential prices in Wales. Drawing on a sample of approximately 192,000 transactions, the capitalisation of energy efficiency ratings into house prices is investigated using two approaches. The first adopts a cross-sectional framework to investigate the effect of EPC rating on price. The second approach applies a repeat-sales methodology to investigate the impact of EPC rating on house price appreciation. Statistically significant positive price premiums are estimated for dwellings in EPC bands A/B (12.8%) and C (3.5%) compared to houses in band D. For dwellings in band E (−3.6%) and F (−6.5%) there are statistically significant discounts. Such effects may not be the result of energy performance alone. In addition to energy cost differences, the price effect may be due to additional benefits of energy efficient features. An analysis of the private rental segment reveals that, in contrast to the general market, low-EPC rated dwellings were not traded at a significant discount. This suggests different implicit prices of potential energy savings for landlords and owner-occupiers.

On the energetics of stratified turbulent mixing, irreversible thermodynamics, Boussinesq models and the ocean heat engine controversy

In this paper, the available potential energy (APE) framework of Winters et al. (J. Fluid Mech., vol. 289, 1995, p. 115) is extended to the fully compressible Navier– Stokes equations, with the aims of clarifying (i) the nature of the energy conversions taking place in turbulent thermally stratified fluids; and (ii) the role of surface buoyancy fluxes in the Munk & Wunsch (Deep-Sea Res., vol. 45, 1998, p. 1977) constraint on the mechanical energy sources of stirring required to maintain diapycnal mixing in the oceans. The new framework reveals that the observed turbulent rate of increase in the background gravitational potential energy GPEr , commonly thought to occur at the expense of the diffusively dissipated APE, actually occurs at the expense of internal energy, as in the laminar case. The APE dissipated by molecular diffusion, on the other hand, is found to be converted into internal energy (IE), similar to the viscously dissipated kinetic energy KE. Turbulent stirring, therefore, does not introduce a new APE/GPEr mechanical-to-mechanical energy conversion, but simply enhances the existing IE/GPEr conversion rate, in addition to enhancing the viscous dissipation and the entropy production rates. This, in turn, implies that molecular diffusion contributes to the dissipation of the available mechanical energy ME =APE +KE, along with viscous dissipation. This result has important implications for the interpretation of the concepts of mixing efficiency γmixing and flux Richardson number Rf , for which new physically based definitions are proposed and contrasted with previous definitions. The new framework allows for a more rigorous and general re-derivation from the first principles of Munk & Wunsch (1998, hereafter MW98)’s constraint, also valid for a non-Boussinesq ocean: G(KE) ≈ 1 − ξ Rf ξ Rf Wr, forcing = 1 + (1 − ξ )γmixing ξ γmixing Wr, forcing , where G(KE) is the work rate done by the mechanical forcing, Wr, forcing is the rate of loss of GPEr due to high-latitude cooling and ξ is a nonlinearity parameter such that ξ =1 for a linear equation of state (as considered by MW98), but ξ <1 otherwise. The most important result is that G(APE), the work rate done by the surface buoyancy fluxes, must be numerically as large as Wr, forcing and, therefore, as important as the mechanical forcing in stirring and driving the oceans. As a consequence, the overall mixing efficiency of the oceans is likely to be larger than the value γmixing =0.2 presently used, thereby possibly eliminating the apparent shortfall in mechanical stirring energy that results from using γmixing =0.2 in the above formula.

Understanding mixing efficiency in the oceans. Do the nonlinearities of the equation of state matter?

There exist two central measures of turbulent mixing in turbulent stratified fluids that are both caused by molecular diffusion: 1) the dissipation rate D(APE) of available potential energy APE; 2) the turbulent rate of change Wr, turbulent of background gravitational potential energy GPEr. So far, these two quantities have often been regarded as the same energy conversion, namely the irreversible conversion of APE into GPEr, owing to the well known exact equality D(APE)=Wr, turbulent for a Boussinesq fluid with a linear equation of state. Recently, however, Tailleux (2009) pointed out that the above equality no longer holds for a thermally-stratified compressible, with the ratio ξ=Wr, turbulent/D(APE) being generally lower than unity and sometimes even negative for water or seawater, and argued that D(APE) and Wr, turbulent actually represent two distinct types of energy conversion, respectively the dissipation of APE into one particular subcomponent of internal energy called the "dead" internal energy IE0, and the conversion between GPEr and a different subcomponent of internal energy called "exergy" IEexergy. In this paper, the behaviour of the ratio ξ is examined for different stratifications having all the same buoyancy frequency N vertical profile, but different vertical profiles of the parameter Υ=α P/(ρCp), where α is the thermal expansion coefficient, P the hydrostatic pressure, ρ the density, and Cp the specific heat capacity at constant pressure, the equation of state being that for seawater for different particular constant values of salinity. It is found that ξ and Wr, turbulent depend critically on the sign and magnitude of dΥ/dz, in contrast with D(APE), which appears largely unaffected by the latter. These results have important consequences for how the mixing efficiency should be defined and measured in practice, which are discussed.

The effect of mechanical stirring on horizontal convection

An important experimental result, as yet poorly understood, is that mechanical stirring can significantly enhance the strength of horizontal convection. A contentious issue is whether this necessarily implies that the mechanical stirring replaces the buoyancy forcing as the main source of energy driving the observed overturning circulation, as has been suggested for the Atlantic meridional overturning circulation (AMOC). In this paper, rigorous energetics considerations and idealized numerical experiments reveal that the rate at which the surface buoyancy forcing supplies energy to the fluid, as measured by the production rate of available potential energy G(APE), does not solely depend upon the buoyancy forcing, as is often implicitly assumed, but also upon the vertical stratification, such that the deeper the thermocline depth, the larger G(APE). This suggests that mechanical stirring enhances horizontal convection because it causes more energy to be extracted from the buoyancy forcing. It does so by enhancing turbulent mixing, which allows surface heating to reach greater depths, which increases the thermocline depth and hence G(APE). This paper therefore proposes a new hypothesis, namely that mechanically stirred horizontal convection and the AMOC are best described as mechanically controlled heat engines.

Mesoscale simulations of organized convection: importance of convective equilibrium

The validity of convective parametrization breaks down at the resolution of mesoscale models, and the success of parametrized versus explicit treatments of convection is likely to depend on the large-scale environment. In this paper we examine the hypothesis that a key feature determining the sensitivity to the environment is whether the forcing of convection is sufficiently homogeneous and slowly varying that the convection can be considered to be in equilibrium. Two case studies of mesoscale convective systems over the UK, one where equilibrium conditions are expected and one where equilibrium is unlikely, are simulated using a mesoscale forecasting model. The time evolution of area-average convective available potential energy and the time evolution and magnitude of the timescale of convective adjustment are consistent with the hypothesis of equilibrium for case 1 and non-equilibrium for case 2. For each case, three experiments are performed with different partitionings between parametrized and explicit convection: fully parametrized convection, fully explicit convection and a simulation with significant amounts of both. In the equilibrium case, bulk properties of the convection such as area-integrated rain rates are insensitive to the treatment of convection. However, the detailed structure of the precipitation field changes; the simulation with parametrized convection behaves well and produces a smooth field that follows the forcing region, and the simulation with explicit convection has a small number of localized intense regions of precipitation that track with the mid-levelflow. For the non-equilibrium case, bulk properties of the convection such as area-integrated rain rates are sensitive to the treatment of convection. The simulation with explicit convection behaves similarly to the equilibrium case with a few localized precipitation regions. In contrast, the cumulus parametrization fails dramatically and develops intense propagating bows of precipitation that were not observed. The simulations with both parametrized and explicit convection follow the pattern seen in the other experiments, with a transition over the duration of the run from parametrized to explicit precipitation. The impact of convection on the large-scaleflow, as measured by upper-level wind and potential-vorticity perturbations, is very sensitive to the partitioning of convection for both cases. © Royal Meteorological Society, 2006. Contributions by P. A. Clark and M. E. B. Gray are Crown Copyright.

Analytical potentials for triatomic molecules from spectroscopic data V. Application to HOX (X=F, Cl, Br, I)

Analytical potential energy functions are reported for HOX (X=F, Cl, Br, I). The surface for HOF predicts two metastable minima as well as the equilibrium configuration. These correspond to HFO (bent) and OHF (linear). Ab initio calculations performed for the HOF surface confirm these predictions. Comparisons are drawn between the two sets of results, and a vibrational analysis is undertaken for the hydrogen bonded OHF species. For HOCl, one further minimum is predicted, corresponding to HClO (bent), the parameters for which compare favourably with those reported from ab initio studies. In contrast, only the equilibrium configurations are predicted to be stable for HOBr and HOI.

Normal coordinates in the methyl halides

The potential‐energy functions found by Chang for the methyl halides have been put into valence‐type form and revised to eliminate inconsistencies and to accord with the true (nontetrahedral) geometry and the normal frequencies (corrected for Fermi resonance and anharmonicity). The resulting valence‐type force constants and normal coordinates are given for light (CH3) and heavy (CD3) chlorides, bromides, and iodides.

Parcel theory in three dimensions and the calculation of SCAPE

Slantwise convective available potential energy (SCAPE) is a measure of the degree to which the atmosphere is unstable to conditional symmetric instability (CSI). It has, until now, been defined by parcel theory in which the atmosphere is assumed to be nonevolving and balanced, that is, two-dimensional. When applying this two-dimensional theory to three-dimensional evolving flows, these assumptions can be interpreted as an implicit assumption that a timescale separation exists between a relatively rapid timescale for slantwise ascent and a slower timescale for the development of the system. An approximate extension of parcel theory to three dimensions is derived and it is shown that calculations of SCAPE based on the assumption of relatively rapid slantwise ascent can be qualitatively in error. For a case study example of a developing extratropical cyclone, SCAPE calculated along trajectories determined without assuming the existence of the timescale separation show large SCAPE values for parcels ascending from the warm sector and along the warm front. These parcels ascend into the cloud head within which there is some evidence consistent with the release of CSI from observational and model cross sections. This region of high SCAPE was not found for calculations along the relatively rapidly ascending trajectories determined by assuming the existence of the timescale separation.