Calculation of Franck-Condon factors including anharmonicity: simulation of the C2 H4+ X̃2B 3u←C2 H4X̃1 Ag band in the photoelectron spectrum of ethylene

Our new simple method for calculating accurate Franck-Condon factors including nondiagonal (i.e., mode-mode) anharmonic coupling is used to simulate the C2H4+X2B 3u←C2H4X̃1 Ag band in the photoelectron spectrum. An improved vibrational basis set truncation algorithm, which permits very efficient computations, is employed. Because the torsional mode is highly anharmonic it is separated from the other modes and treated exactly. All other modes are treated through the second-order perturbation theory. The perturbation-theory corrections are significant and lead to a good agreement with experiment, although the separability assumption for torsion causes the C2 D4 results to be not as good as those for C2 H4. A variational formulation to overcome this circumstance, and deal with large anharmonicities in general, is suggested

Variational calculation of vibrational linear and nonlinear optical properties

A variational approach for reliably calculating vibrational linear and nonlinear optical properties of molecules with large electrical and/or mechanical anharmonicity is introduced. This approach utilizes a self-consistent solution of the vibrational Schrödinger equation for the complete field-dependent potential-energy surface and, then, adds higher-level vibrational correlation corrections as desired. An initial application is made to static properties for three molecules of widely varying anharmonicity using the lowest-level vibrational correlation treatment (i.e., vibrational Møller-Plesset perturbation theory). Our results indicate when the conventional Bishop-Kirtman perturbation method can be expected to break down and when high-level vibrational correlation methods are likely to be required. Future improvements and extensions are discussed

Basis set and electron correlation effects on initial convergence for vibrational nonlinear optical properties of conjugated organic molecules

The level of ab initio theory which is necessary to compute reliable values for the static and dynamic (hyper)polarizabilities of three medium size π-conjugated organic nonlinear optical (NLO) molecules is investigated. With the employment of field-induced coordinates in combination with a finite field procedure, the calculations were made possible. It is stated that to obtain reasonable values for the various individual contributions to the (hyper)polarizability, it is necessary to include electron correlation. Based on the results, the convergence of the usual perturbation treatment for vibrational anharmonicity was examined

The First World War and coal trade geography in Latin America and the Caribbean (1890-1930)

This paper aims to illustrate the dynamics of coal trade between Latin America and its main trade partners, i.e. the USA, Great Britain and Germany, before and after the enormous disruption caused by the First World War. The coal trade was used as an indicator of modernization for Latin American countries, given that oil was at that time of secondary importance. Energy imports have determined the possibilities of each Latin American country in its process of development. Here we address this question and place special emphasis on supply channels, concluding that the trade link with main suppliers was of key significance. Although this was very clear by the end of the period, the process had started well before the First World War, at least for the majority of LA&C countries. These points are developed through a gravity model applied to the bilateral coal trade. The importance of the market supplier share is addressed through cluster methodologies.

European integration, FDI and the internal geography of trade : evidence from Western European border regions

In this paper we use a gravity model to study the trade performance of French and Spanishborder regions relatively to non-border regions, over the past two decades. We find that,controlling for their size, proximity and location characteristics, border regions trade onaverage between 62% and 193% more with their neighbouring country than other regions,and twice as much if they are endowed with good cross border transport infrastructures.Despite European integration, however, this trade outperformance has fallen for the mostperipheral regions within the EU. We show that this trend was linked in part to a shift in the propensity of foreign investors to move their affiliates from the regions near their home market to the regions bordering the EU core.

Stochastic semiclassical gravity

In the first part of this paper, we show that the semiclassical Einstein-Langevin equation, introduced in the framework of a stochastic generalization of semiclassical gravity to describe the back reaction of matter stress-energy fluctuations, can be formally derived from a functional method based on the influence functional of Feynman and Vernon. In the second part, we derive a number of results for background solutions of semiclassical gravity consisting of stationary and conformally stationary spacetimes and scalar fields in thermal equilibrium states. For these cases, fluctuation-dissipation relations are derived. We also show that particle creation is related to the vacuum stress-energy fluctuations and that it is enhanced by the presence of stochastic metric fluctuations.

Pair production by and electric field in (1+1)-dimensional de Sitter space

We use the method of Bogolubov transformations to compute the rate of pair production by an electric field in (1+1)-dimensional de Sitter space. The results are in agreement with those obtained previously using the instanton methods. This is true even when the size of the instanton is comparable to the size of the de Sitter horizon.

Open inflation and the singulary boundary

The singularity in the Hawking-Turok model of open inflation has some appealing properties, such as the fact that its action is integrable. Also, if one thinks of the singularity as the boundary of spacetime, then the Gibbons-Hawking term is nonvanishing and finite. Here, we consider a model where the gravitational and scalar fields are coupled to a dynamical membrane. The singular instanton can then be obtained as the limit of a family of no-boundary solutions where both the geometry and the scalar field are regular. Using this procedure, the contribution of the singularity to the Euclidean action is just 1/3 of the Gibbons-Hawking term. Unrelated to this issue, we also point out that the singularity acts as a reflecting boundary for scalar perturbations and gravity waves. Therefore, the quantization of cosmological perturbations seems to be well posed in this background.

Large N phases, gravitational instantons and the nuts and bolts of AdS holography

Recent results in the literature concerning holography indicate that the thermodynamics of quantum gravity (at least with a negative cosmological constant) can be modeled by the large N thermodynamics of quantum field theory. We emphasize that this suggests a completely unitary evolution of processes in quantum gravity, including black hole formation and decay, and even more extreme examples involving topology change. As concrete examples which show that this correspondence holds even when the space-time is only locally asymptotically AdS, we compute the thermodynamical phase structure of the AdS-Taub-NUT and AdS-Taub-bolt spacetimes, and compare them to a (2+1)-dimensional conformal field theory (at large N) compactified on a squashed three-sphere and on the twisted plane.

Exact gravitational shockwaves and Planckian scattering on branes

We obtain a solution describing a gravitational shock wave propagating along a Randall-Sundrum brane. The interest of such a solution is twofold: on the one hand, it is the first exact solution for a localized source on a Randall-Sundrum three-brane. On the other hand, one can use it to study forward scattering at Planckian energies, including the effects of the continuum of Kaluza-Klein modes. We map out the different regimes for the scattering obtained by varying the center-of-mass energy and the impact parameter. We also discuss exact shock waves in ADD scenarios with compact extra dimensions.

Cosmological perturbations from stochastic gravity

In inflationary cosmological models driven by an inflaton field the origin of the primordial inhomogeneities which are responsible for large-scale structure formation are the quantum fluctuations of the inflaton field. These are usually calculated using the standard theory of cosmological perturbations, where both the gravitational and the inflaton fields are linearly perturbed and quantized. The correlation functions for the primordial metric fluctuations and their power spectrum are then computed. Here we introduce an alternative procedure for calculating the metric correlations based on the Einstein-Langevin equation which emerges in the framework of stochastic semiclassical gravity. We show that the correlation functions for the metric perturbations that follow from the Einstein-Langevin formalism coincide with those obtained with the usual quantization procedures when the scalar field perturbations are linearized. This method is explicitly applied to a simple model of chaotic inflation consisting of a Robertson-Walker background, which undergoes a quasi-de Sitter expansion, minimally coupled to a free massive quantum scalar field. The technique based on the Einstein-Langevin equation can, however, deal naturally with the perturbations of the scalar field even beyond the linear approximation, as is actually required in inflationary models which are not driven by an inflaton field, such as Starobinsky¿s trace-anomaly driven inflation or when calculating corrections due to nonlinear quantum effects in the usual inflaton driven models.

Stability of de Sitter spacetime under isotropic perturbations in semiclassical gravity

A spatially flat Robertson-Walker spacetime driven by a cosmological constant is nonconformally coupled to a massless scalar field. The equations of semiclassical gravity are explicitly solved for this case, and a self-consistent de Sitter solution associated with the Bunch-Davies vacuum state is found (the effect of the quantum field is to shift slightly the effective cosmological constant). Furthermore, it is shown that the corrected de Sitter spacetime is stable under spatially isotropic perturbations of the metric and the quantum state. These results are independent of the free renormalization parameters.

Gravity in the Randall-Sundrum brane world

We discuss the weak gravitational field created by isolated matter sources in the Randall-Sundrum brane world. For the case of a single wall of positive tension, the field stays localized near the wall if the source is stationary. We calculate the leading Kaluza-Klein corrections to the linearized gravitational field of a nonrelativistic spherical object, which is different from the Schwarzschild solution at large distances. In the case of two branes of opposite tension, linearized Brans-Dicke (BD) gravity is recovered on either wall, with different BD parameters. On the wall with positive tension the BD parameter is larger than 3000 provided that the separation between walls is larger than 4 times the AdS radius. The gravitational field due to shadow matter is also considered.

Quantization of AdS3 black holes in external fields: semiclassical results from pure gravity

(2+1)-dimensional anti-de Sitter (AdS) gravity is quantized in the presence of an external scalar field. We find that the coupling between the scalar field and gravity is equivalently described by a perturbed conformal field theory at the boundary of AdS3. This allows us to perform a microscopic computation of the transition rates between black hole states due to absorption and induced emission of the scalar field. Detailed thermodynamic balance then yields Hawking radiation as spontaneous emission, and we find agreement with the semiclassical result, including greybody factors. This result also has application to four and five-dimensional black holes in supergravity.

The First World War and coal trade geography in Latin America and the Caribbean (1890-1930)

This paper aims to illustrate the dynamics of coal trade between Latin America and its main trade partners, i.e. the USA, Great Britain and Germany, before and after the enormous disruption caused by the First World War. The coal trade was used as an indicator of modernization for Latin American countries, given that oil was at that time of secondary importance. Energy imports have determined the possibilities of each Latin American country in its process of development. Here we address this question and place special emphasis on supply channels, concluding that the trade link with main suppliers was of key significance. Although this was very clear by the end of the period, the process had started well before the First World War, at least for the majority of LA&C countries. These points are developed through a gravity model applied to the bilateral coal trade. The importance of the market supplier share is addressed through cluster methodologies.