This paper addresses the problem of the separation of rotational and internal motion. It introduces the concept of average angular velocity as the moment of inertia weighted average of particle angular velocities. It extends and elucidates the concept of Jellinek and Li (1989) of separation of the energy of overall rotation in an arbitrary (non-linear) N -particle system. It generalizes the so ...

A full dimensional quasiclassical trajectory study of the OH+SO reaction is presented with the aim of investigating the role of the reactants rotational energy in the reactivity. Different energetic combinations with one and both reactants rotationally excited are studied. A passive method is used to correct zero-point-energy leakage in the classical calculations. The reactive cross sections, f...

We report quantum dynamics calculations of rotational and vibrational energy transfer in collisions between two para-H(2) molecules over collision energies spanning from the ultracold limit to thermal energies. Results obtained using a recent full-dimensional H(2)-H(2) potential energy surface (PES) developed by Hinde [J. Chem. Phys. 128, 154308 (2008)] are compared with those derived from the ...

We present the implementation of a new crossed-molecular beam, velocity-map ion-imaging apparatus, optimized for collisions of electronically excited molecules. We have applied this apparatus to rotational energy transfer in NO(A(2)Σ(+), v = 0, N = 0, j = 0.5) + Ar collisions, at an average energy of 525 cm(-1). We report differential cross sections for scattering into NO(A(2)Σ(+), v = 0, N' = ...

Computational methods available for the calculation of relative and absolute binding affinities (free energy simulations, continuum electrostatics, linear interaction energy approximations, and empirical solvation models) are reviewed together with recent applications to biological systems. The decomposability of the binding free energy into physically meaningful components is examined and resu...

Analysis of the hot H2 16O spectrum, presented by Polyansky et al. (1996, J. Mol. Spectrosc. 176, 305-315), is extended to higher vibrational states. Three hundred thirty mainly strong lines are assigned to pure rotational transitions in the (100), (001), and (020) vibrational states. These lines, which involve significantly higher rotational energy levels than were known previously, are assign...

Under standard conditions reaction yields are connected with terms like free energy differences and thermal distributions. However, many modern experimental techniques, such as supersonic beam expansion or matrix isolation, deal with cryogenic temperatures and isolated reactants in inert clusters or solid matrices. Under these conditions the photochemical reaction mechanism is in many cases str...

Single photon dissociation of bromoform using synchrotron radiation has been investigated by Fourier transform visible fluorescence spectroscopy (FTVIS). The photodissociation of bromoform in the 12-18 eV energy range results in several products, among which are the CH(A2Delta) and CH(B2Sigma) radicals. Vibrational and rotational state distributions of the CH(A2Delta) are determined from their ...