Insight into the halogen-bond nature of noble gas-chlorine systems by molecular beam scattering experiments, ab initio calculations and charge displacement analysis.

We have carried out molecular-beam scattering experiments and high-level ab initio investigations on the potential energy surfaces of a series of noble-gas-Cl2 adducts. This effort has permitted the construction of a simple, reliable and easily generalizable analytical model potential formulation, which is based on a few physically meaningful parameters of the interacting partners and transparently shows the origin, strength, and stereospecificity of the various interaction components. The results demonstrate quantitatively beyond doubt that the interaction between a noble-gas (Ng) atom - even He - and Cl2 in a collinear configuration is characterized by weak halogen bond (XB) formation, accompanied by charge transfer (CT) from the Ng to chlorine. This characteristic, which stabilizes the adduct, rapidly disappears on going towards the T-shaped configuration, dominated by pure van der Waals (vdW) forces. Similarly, a pure vdW interaction takes place - with no CT component in any configuration - if Cl2 is present in the lowest πg* → σu* excited state, because the change in electron density that accompanies the excitation eliminates the Cl2 polar flattening and σ hole, making the XB interaction inaccessible.

Diel oscillation in the optical activity of carotenoids in the absorption spectrum of Nannochloropsis.

In this paper we show that the absorption spectrum of the microalgae Nannochloropsis oceanica exhibits changes in response to the modulation of incident light. A model was used to analyze the contribution of different active pigments to the total absorption in the photosynthetically active radiation region and suggested consistent diel oscillations in the optical activity of carotenoids.

The interaction of CCl4 with Ng (Ng = He, Ne, Ar), O2, D2O and ND3: rovibrational energies, spectroscopic constants and theoretical calculations.

This investigation generated rovibrational energies and spectroscopic constants for systems of CCl4 with Ng (Ng = He, Ne, Ar), O2, D2O and ND3 from scattering experimental data, and the results presented are of interest for microwave spectroscopy studies of small halogenated molecules. The rovibrational spectra were obtained through two different approaches (Dunham and DVR) within the improved Lennard Jones (ILJ) model. Spectra were also generated within ordinary Lennard Jones and deviations suggest that the ILJ model should be preferred due to interactions beyond dispersion forces presented in these systems. Data from the literature and additional high level quantum mechanical calculations presented in this work show that these systems should not be considered as van der Waals complexes due to halogen bonding (HB) interactions, and this is especially true for the CCl4-D2O and CCl4-ND3 complexes. The charge displacement from the latter systems are one order of magnitude higher than the values from literature for CCl4 and He, Ne, Ar and O2 systems, and show significant deviations between DFT and Hartree-Fock values not previously reported in the literature.

Low-Temperature Seebeck Coefficients for Polaron-Driven Thermoelectric Effect in Organic Polymers.

We report the results of electronic structure coupled to molecular dynamics simulations on organic polymers subject to a temperature gradient at low-temperature regimes. The temperature gradient is introduced using a Langevin-type dynamics corrected for quantum effects, which are very important in these systems. Under this condition we were able to determine that in these no-impurity systems the Seebeck coefficient is in the range of 1-3 µV/K. These results are in good agreement with reported experimental results under the same low-temperature conditions.

Stability Diagrams for Paul Ion Traps Driven by Two-Frequencies.

In this paper, we present and discuss stability diagrams for Paul traps driven by two ac voltages. In contrast to a typical Paul trap, here we suggest a secondary ac voltage whose frequency is twice the frequency of the primary one. The ratio between their amplitudes can be used to expand the region of stability and to access different states of motion of trapped ions. This provides a further mechanism to trap, cool, and manipulate single ions and also to improve the experimental framework where ion clouds and crystals can be prepared and controlled. Such approach opens the possibility of designing more sophisticated trapping architectures, leading to a wide variety of applications on ion trap research and mass analysis techniques.

H2O-CH4 and H2S-CH4 complexes: a direct comparison through molecular beam experiments and ab initio calculations.

New molecular beam scattering experiments have been performed to measure the total (elastic plus inelastic) cross sections as a function of the velocity in collisions between water and hydrogen sulfide projectile molecules and the methane target. Measured data have been exploited to characterize the range and strength of the intermolecular interaction in such systems, which are of relevance as they drive the gas phase molecular dynamics and the clathrate formation. Complementary information has been obtained by rotational spectra, recorded for the hydrogen sulfide-methane complex, with a pulsed nozzle Fourier transform microwave spectrometer. Extensive ab initio calculations have been performed to rationalize all the experimental findings. The combination of experimental and theoretical information has established the ground for the understanding of the nature of the interaction and allows for its basic components to be modelled, including charge transfer, in these weakly bound systems. The intermolecular potential for H2S-CH4 is significantly less anisotropic than for H2O-CH4, although both of them have potential minima that can be characterized as 'hydrogen bonded'.

Rovibrational energies and spectroscopic constants for H2O-Ng complexes.

In this work, rovibrational energies and spectroscopic constants for the water -Ng complexes (Ng = He, Ne, Ar, Kr and Xe) were calculated through two different approaches (by solving the Nuclear Schrödinger equation and by applying the Dunham's method) and using two different potential energy curves (PEC). These PEC were determined using potential parameters obtained through molecular beam scattering experiments and accurate theoretical calculation, respectively. It was found that the theoretical rovibrational energies are in a good agreement (only for the lowest numbers of vibrational states) with those obtained through experimental PEC. Another important conclusions was regarding the calculated first two rovibrational energies for the H 2 O-Ar system, that are in a good agreement with the experimental data.

The spontaneous synchronized dance of pairs of water molecules.

Molecular beam scattering experiments have been performed to study the effect of long-range anisotropic forces on the collision dynamics of two small polar molecules. The main focus of this paper is on water, but also ammonia and hydrogen sulphide molecules have been investigated, and some results will be anticipated. The intermolecular distances mainly probed are of the order of 1 nm and therefore much larger than the molecular dimensions. In particular, we have found that the natural electric field gradient, generated by different spatial orientations of the permanent electric dipoles, is able to promote the transformation of free rotations into coupled pendular states, letting the molecular partners involved in the collision complex swinging to and fro around the field direction. This long-ranged concerted motion manifested itself as large increases of the magnitude of the total integral cross section. The experimental findings and the theoretical treatment developed to shed light on the details of the process suggest that the transformation from free rotations to pendular states depends on the rotational level of both molecules, on the impact parameter, on the relative collision velocity, on the dipole moment product and occurs in the time scale of picoseconds. The consequences of this intriguing phenomenon may be important for the interpretation and, in perspective, for the control of elementary chemical and biological processes, given by polar molecules, ions, and free radicals, occurring in several environments under various conditions.

Exciton dissociation and charge carrier recombination processes in organic semiconductors.

Exciton dissociation and charge recombination processes in organic semiconductors, with thermal effects taken into account, are described in this paper. Here, we analyzed the mechanisms of polaron-excitons dissociation into free charge carriers and the consequent recombination of those carriers under thermal effects on two parallel π-conjugated polymers chains electronically coupled. Our results suggest that exciton dissociation in a single molecule give rise to localized, polaron-like charge carrier. Besides, we concluded that in the case of interchain processes, the bimolecular polaron recombination does not lead to an usual exciton state. Rather, this type of recombination leads to an oscillating dipole between the two chains. The recombination time obtained here for these processes are in agreement with the experimental results. Finally, our results show that temperature effects are essential to the relaxation process leading to polaron formation in a single chain, as in the absence of temperature, this process was not observed. In the case of two chains, we conclude that temperature effects also help the bimolecular recombination process, as observed experimentally.

Molecular-beam study of the ammonia-noble gas systems: characterization of the isotropic interaction and insights into the nature of the intermolecular potential.

We report new high resolution molecular beam experiments aimed at characterizing the intermolecular interaction in the NH(3)-Ng (Ng = He, Ne, Ar, Kr, Xe) weakly bound complexes. Integral cross section data are obtained over a sufficiently wide velocity range and with rotationally hot NH(3) molecules to produce (except for the NH(3)-He case) a well resolved "glory" quantum interference pattern. Data analysis, carried out by employing a recently proposed potential model, allows unique information on the absolute scale of the intermolecular interaction to be obtained both at long range and at the equilibrium distance. An extensive and internally consistent comparison with the behavior of the corresponding Kr-Ng systems is exploited in order to identify those cases where an interaction component due to charge transfer effects provides an appreciable intermolecular bond stabilization that is clearly distinct from and must be added to the standard van der Waals plus induction picture. The results of the present investigation extend the phenomenology of perturbative charge transfer effects in gas phase complexes involving hydrogenated molecules.

Thermal rate constant calculation of the NF + F reactive system multiple arrangements.

In this work we analyzed the multiple channels of the reaction NF+F through the evaluation of thermal rate constants with both Wigner and Eckart tunneling corrections. Minimum energy paths and intrinsic reaction coordinates of the systems were obtained and accurately studied in order to ensure the consistency of our results. Specifically, we investigated the NF + F = N + F(2), NF + F = NF + F, and NF(2) = NF + F, reactive systems. As experimental data are available for the latter reaction, we were able to conclude that our thermal rate constants are in agreement for a wide range of temperatures. The here performed study is relevant to the understanding of the decomposition process of nitrogen trifluoride (NF(3)).

Charge-transfer energy in the water-hydrogen molecular aggregate revealed by molecular-beam scattering experiments, charge displacement analysis, and ab initio calculations.

Integral cross-section measurements for the system water-H(2) in molecular-beam scattering experiments are reported. Their analysis demonstrates that the average attractive component of the water-H(2) intermolecular potential in the well region is about 30% stronger than dispersion and induction forces would imply. An extensive and detailed theoretical analysis of the electron charge displacement accompanying the interaction, over several crucial sections of the potential energy surface (PES), shows that water-H(2) interaction is accompanied by charge transfer (CT) and that the observed stabilization energy correlates quantitatively with CT magnitude at all distances. Based on the experimentally determined potential and the calculated CT, a general theoretical model is devised which reproduces very accurately PES sections obtained at the CCSD(T) level with large basis sets. The energy stabilization associated with CT is calculated to be 2.5 eV per electron transferred. Thus, CT is shown to be a significant, strongly stereospecific component of the interaction, with water functioning as electron donor or acceptor in different orientations. The general relevance of these findings for water's chemistry is discussed.

Theoretical temperature dependence of the charge-carrier mobility in semiconducting polymers.

We present a theory of the temperature and electric field dependence on the mobility of polarons in conjugated polymers in terms of a tight-binding and stochastic approach. The polaron mobility is shown to have a strong dependence on the electric field, with two distinct regimes of temperature dependence. Lattice thermal oscillations enhance polaron mean velocity for electric fields of 1.0 mV/A or higher. In contrast, its mobility is damped by thermal oscillations under weaker electric fields. This semiconductor/metallic analogous behavior comes from the difference between the inertial content acquired by polarons under stronger/weaker electric fields. These new results and their analysis shed new light on several experimental controversies.

Beyond the Lennard-Jones model: a simple and accurate potential function probed by high resolution scattering data useful for molecular dynamics simulations.

Scattering data, measured for rare gas-rare gas systems under high angular and energy resolution conditions, have been used to probe the reliability of a recently proposed interaction potential function, which involves only one additional parameter with respect to the venerable Lennard-Jones (LJ) model and is hence called Improved Lennard-Jones (ILJ). The ILJ potential eliminates most of the inadequacies at short- and long-range of the LJ model. Further reliability tests have been performed by comparing calculated vibrational spacings with experimental values and calculated interaction energies at short-range with those obtained from the inversion of gaseous transport properties. The analysis, extended also to systems involving ions, suggests that the ILJ potential model can be used to estimate the behavior of unknown systems and can help to assess the different role of the leading interaction components. Moreover, due to its simple formulation, the physically reliable ILJ model appears to be particularly useful for molecular dynamics simulations of both neutral and ionic systems.