D. Van Neck

A novel force-field development strategy is proposed that tackles the well-known difficulty of parameter correlations arising in a conventional least-squares optimization. In the first step of the new gradient curves method (GCM), continuity criteria are imposed to transform the raw multidimensional ab initio training data to distinct sets of one-dimensional data, each associated with an individual energy term. In the second step, the transformed data suggest suitable analytical expressions, and the parameters in these expressions are fitted to the transformed data; that is, one does not have to postulate a priori analytical expressions for the force-field energy terms. This approach facilitates the derivation of valence terms. Benchmarks have been performed on a set of small molecules. The results show that the new method yields physically acceptable energy terms exactly when a conventional parametrization would suffer from parameter correlations, that is, when an increasing number of redundant internal coordinates is used in the force-field model. The generic treatment of parameter correlations in the proposed method facilitates an intuitive physical interpretation of the individual terms in the force-field expression, which is a prerequisite for the transferability of force-field models.

The electron propagator is calculated for a set of closed-shell atoms using GW-like self-energies that contain the coupling of single-particle degrees of freedom with excited states in the framework of the random phase approximation. The effect of including exchange diagrams is investigated. Calculations are performed in the Hartree-Fock (HF) basis of the neutral atom. The HF continuum is taken into account using a discretization procedure, and the basis set limit is estimated using a systematic increase of basis set size. We check the approximation of taking the self-energy diagonal in the HF basis, and to what extent the extended Koopman’s theorem is fulfilled using an approximate self-energy. Finally we try to model the information contained in the propagator in terms of a functional containing Hartree-Fock quantities and demonstrate the feasibility of simultaneously reproducing the correlation and ionization energy of an underlying ab initio model.

Large-amplitude motions, particularly internal rotations, are known to affect substantially thermodynamic functions and rate constants of reactions in which flexible molecules are involved. Up to now all methods for computing the partition functions of these motions rely on the Pitzer approximation of more than 50 years ago, in which the large-amplitude motion is treated in complete independence of the other (vibrational) degrees of freedom. In this paper an extended hindered-rotor model (EHR) is developed in which the vibrational modes, treated harmonically, are correctly separated from the large-amplitude motion and in which relaxation effects (the changes in the kinetic-energy matrix and potential curvature) are taken into account as one moves along the large-amplitude path. The model also relies on a specific coordinate system in which the Coriolis terms vanish at all times in the Hamiltonian. In this way an increased level of consistency between the various internal modes is achieved, as compared with the more usual hindered-rotor (HR) description. The method is illustrated by calculating the entropies and heat capacities on 1,3-butadiene and 1-butene (with, respectively, one and two internal rotors) and the rate constant for the addition reaction of a vinyl radical to ethene. We also discuss various variants of the one-dimensional hindered-rotor scheme existing in the literature and its relation with the EHR model. It is argued why in most cases the HR approach is already quite successful.

In this Letter, we unravel the origin of the good-behavior of the one-dimensional hindered rotor model to describe the partition function and derived thermodynamic properties of n-alkanes. The simplified uncoupled model predicts entropies of n-alkanes up to decane with a standard deviation less than 1% (P. Vansteenkiste, V. Van Speybroeck, G.B. Marin, M. Waroquier, J. Phys. Chem. A 107 (2003) 3139). Application of a fully coupled scheme for the internal rotations present in pentane and hexane gives a justification of the success of the uncoupled hindered rotor model based on microscopic grounds. The success of the separable rotor model is due to fortuitous cancellation of errors and cannot be generalized.