A recently introduced bond–bond formulation of the intermolecular interaction has been extended to six‐atom systems to the end of assembling a new potential energy surface (PES) and has been incorporated into a grid empowered simulator able to handle the modeling of the CO2 + CO2 processes. The proposed PES is full dimensional and accounts for the dependence of the intermolecular interaction on some basic physical properties of the colliding partners, including modulations induced by the monomer deformation. The used analytical formulation of the interaction involves a limited number of parameters, each having a clear physical meaning. Guess values for these parameters can also be obtained from analytical correlation formulae. Such estimates can then be fine tuned by exploiting experimental and theoretical information. The resulting PES well describes stretched and bent asymptotic CO2 monomers as well as the CO2–CO2 interaction in the most and less stable configurations. On this potential massive quasiclassical elastic and inelastic detailed scattering trajectories have been integrated, by exploiting the innovative computational technologies of the grid. The efficiency of the approach used and the reliability of the estimates of the dynamical properties obtained in this way is such that we can now plan a systematic evaluation of the state specific rate coefficient matrix elements needed for space craft reentry modeling. Here, we present probabilities and cross sections useful to rationalize some typical mechanisms characterizing the vibrational transitions of the CO2 + CO2 system on the flexible monomer proposed PES. On such PES, the key dynamical outcomes are: (a) there is a strong energy interchange between symmetric stretching of the reactants and bending of the products (and viceversa) while asymmetric stretching is strongly adiabatic (b) reactant energy is more efficiently allocated (with respect to the rigid monomers PES) as product vibration when reactant stretching modes are excited while the contrary is true when the reactant bending mode is excited. © 2012 Wiley Periodicals, Inc.

A quantum chemical exploration is reported on the interaction potentials of H2O2 with the rare gases, He, Ne, Ar, Kr, and Xe. Hydrogen peroxide (the simplest example of chiral molecule in its equilibrium geometry) is modeled as rigid except for the torsional mode around the O-O bond. However, on the basis of previous work (Maciel, G. S.; et al. Chem. Phys. Lett. 2006 432, 383), the internal mode description is based, rather than on the vectors of the usual valence picture, on the orthogonal local representation, which was demonstrated useful for molecular dynamics simulations, because the torsion around the vector joining the center-of-mass of the two OH radicals mimics accurately the adiabatic reaction path for chirality changing isomerization, following the torsional potential energy profile from equilibrium through the barriers for the trans and cis geometries. The basic motivation of this work is the determination of potential energy surfaces for the interactions to be used in classical and quantum simulations of molecular collisions, specifically those leading to chirality changes of possible relevance in the modeling of prebiotic phenomena. Particular attention is devoted to the definition of coordinates and expansion formulas for the potentials, allowing for a faithful representation of geometrical and symmetry properties of these systems, prototypical of the interaction of an atom with a floppy molecule.

The structural and energetic properties of the H 2 S 2 molecule have been studied using density functional theory, second-order Møller-Plesset method, and coupled cluster theory with several basis sets. In order to extend previous work on intra-and intermolecular dynamics of the chirality changing modes for H 2 O 2 and its derivatives, our focus has been on the torsion around the S-S bond, along with an extensive characterization of the intermolecular potentials of H 2 S 2 with the rare gases ͑He, Ne, Ar, and Kr͒. Use is made of previously defined coordinates and expansion formulas for the potentials which allow for a faithful representation of geometrical and symmetry properties of these systems that involve the interaction of an atom with a floppy molecule. The potential energy surfaces obtained in this work are useful for classical and quantum mechanical simulations of molecular collisions responsible for chirality changing processes of possible interest in the modeling of prebiotic phenomena.

The modeling of atmospheric gas, interacting with the space vehicles in re-entry conditions in planetary exploration missions, requires large set of scattering data for all those elementary processes occurring in the system. A fundamental aspect of re-entry problems is represented by the strong nonequilibrium conditions met in the atmospheric plasma close to the surface of the thermal shield, where numerous interconnected relaxation processes determine the evolution of the gaseous system towards the equilibrium conditions. A central role is played by the vibrational exchanges of energy, so that collisional processes involving vibrationally excited molecules assume a particular importance. In the present paper, theoretical calculations of complete sets of vibrationally state-resolved cross sections and rate coefficients are reviewed, focusing on the relevant classes of collisional processes: resonant and non-resonant electronimpact excitation of molecules, atom-diatom and molecule-molecule collisions as well as gas-surface interaction. In particular, collisional processes involving atomic and molecular species, relevant to Earth (N 2 ,O 2 ,NO), Mars (CO 2 ,CO,N 2) and Jupiter (H 2 ,He) atmospheres are considered.

The exploration of alternative roads that open to molecules with sufficient energy to yield different products permits prediction and eventually control of the outcomes of chemical reactions. Advanced imaging techniques for monitoring laser-induced photodissociation are here combined with dynamical simulations, involving ample sets of classical trajectories generated on a quantum chemical potential energy surface. Methyl formate, HCOOCH3, is photodissociated at energies near the triple fragmentation threshold into H, CO and OCH3. Images of velocity and rotational distributions of CO exhibit signatures of alternative routes, such as those recently designated as transition-state vs. roaming-mediated. Furthermore, a demonstration of the triple fragmentation route is given, and also confirmed by H-atom product imaging and FTIR time-resolved spectra of the intermediate HCO radical. In addition, the relevance of nonadiabatic transitions promoted by a conical intersection is clarified by simulations as the privileged "reactivity funnel" of organic photochemistry, whereby the outcomes of molecular photoexcitation are delivered to electronic ground states.

Graphynes are porous derivatives of graphene that can be considered as ideal 2D nanofilters. Here, we investigate by theoretical methods graphtriyne multilayers, proposing them as membranes featuring pores of subnanometer size suitable for CO 2 /N 2 separation and CO 2 uptake. The potential energy surfaces, representing the intermolecular interactions within the CO 2 /N 2 gaseous mixtures and between the graphtriyne layers and the molecules, have been formulated in an internally consistent way, by adopting potential models far more accurate than the traditional Lennard-Jones functions, routinely used to predict static and dynamical properties of matter. The new force fields so obtained and tested on accurate ab initio calculations have been used to perform extensive molecular dynamics simulations of membrane selectivity and adsorption. The accuracy of the potentials granted a quantitative description of the interactions and realistic results for the dynamics under a wide range of conditions of applied interest, indicating a single-layer permeation ratio CO 2 /N 2 of 4.25 (meaning that permeations of CO 2 are typically 4.25 times those of N 2). At low pressure, graphtriyne bilayer membranes exhibit good performances as a molecular sieving candidate for postcombustion CO 2 separation because of a high permeance and a relatively good selectivity. On the other hand, graphtriyne trilayer membranes present a relatively high interlayer adsorption selectivity and a high CO 2 uptake. Such properties make these graphyne nanostructures versatile materials competitive with other carbonbased adsorbing membranes suitable to cope with post-combustion CO 2 emissions. Moreover, guidelines for the extension of the proposed methodology to carbon nanostructures and other gaseous mixtures of relevance for atmosphere and combustion are also provided.

Rigorous and complete definitions of two partitions and one expansion for the kinetic energy of a general N-particle classical system are given. Our recent work, which also provides examples of applications to the molecular dynamics of nanoaggregates, based on computer programs formulated on the basis of the theory presented here, is extended to cover arbitrary physical space dimensions. The partitions and the expansion are in terms of quantities conceived to be instantaneous phase-space invariants-a far-reaching generalization of integrals of the motion. These quantities are introduced setting out as starting points the position matrix Z of the system and the time derivative of Z. In the simplest case, the matrix Z contains the mass-scaled Cartesian coordinates of the N particles. From the position matrix, the kinematic rotations naturally arise through orthogonal transformations, as a concept "dual" to the ordinary physical rotations. The physical meaning of each partition ͑expansion͒ term is clearly described and emphasized, and formulas for the various quantities are provided as well as inequalities among them. Proofs are presented making extensive use of the singular value decomposition ͑SVD͒ of matrices and of the signed SVD, an extended version overcoming possible singularities for particular values of N.HYPERANGULAR MOMENTA AND ENERGY PARTITIONS… PHYSICAL REVIEW A 72, 033201 ͑2005͒ 033201-3 ͑a͒ If J = 0 thenholds for arbitrary J. ͑c͒ If N ജ d + 1 and all the d singular values of the position matrix Z are positive, thenso that E out ജ E in , E out ജ T rot , and E coupl ഛ 0 for K =0.͑bЈ͒ The inequality

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