An Experimental Model on the Biomechanical Behaviour of the Flexor Tendons in New Zealand Rabbits.

BACKGROUND: In order to introduce new pharmacological agents with the intent to inhibit the adhesion formation, it is important to test such products on laboratory animals under a protocol that can evaluate the quantitative and qualitative aspects of healing of the tendons. Most experimental models focus on the tensile strength and histological analysis of the tendons, failing to sufficiently quantify the degree of the adhesion formation. METHODS: The experiment included six male New Zealand rabbits that underwent surgery of their right forepaws. The deep flexor tendon of the middle finger was transected and repaired and after six weeks the rabbits were killed. In order to assess the extent of adhesions, the functional stiffness of the tendons and the range of motion of the specimens' fingers was studied using a tensile testing machine. The setup used allowed the simultaneous recording of the specimens' motion and the pulling force values. RESULTS: The mean values of the left and right forepaws were expressed in the same chart showing a clear difference between the operated and non operated forepaws. CONCLUSIONS: Using a relatively simple set up in the laboratory we had the chance to focus on a more elaborate analysis of the data with the help of low cost and accessible software.

Analysis of Partition Functions for Metallocenes: Ferrocene, Ruthenocene, and Osmocene.

We present a calculation of the torsional potential of the three metallocenes of the iron group, that is, ferrocene, ruthenocene, and osmocene, calculated with the GAUSSIAN program suite. Both a variational method (through computation of the exact energy levels) and our Chebyshev imaginary time propagation method are used to calculate the hindered rotation partition function, demonstrating the efficiency of the Chebyshev scheme. The transition from a semirigid through a hindered rotor to the free rotor regime is demonstrated, and the effect of the hindered rotation (as opposed to a harmonic) treatment on the thermodynamics of metallocenes is demonstrated.

Methods for Calculating Partition Functions of Molecules Involving Large Amplitude and/or Anharmonic Motions.

We present a method for calculating partition functions taking into account anharmonic contributions for systems involving both small-amplitude vibrations and hindered rotations. The Wang-Landau scheme is used in the first case, while two alternative schemes are used for hindered rotation based on imaginary time propagation and fitting of the exact energy levels as a function of quantum number. These two schemes are shown to be complementary in their ranges of applicability (in terms of the torsional rotational constant and the relevant potential). Partition functions for four different molecules are calculated and compared to simpler ones obtained using a harmonic model.

Nonadiabatic photodynamics of phenol on a realistic potential energy surface by a novel multilayer Gaussian MCTDH program.

We report the main features of a new implementation of the Gaussian Multi-Configuration Time-Dependent Hartree (G-MCTDH) model. The code allows effective computations of time-dependent phenomena, including calculation of vibronic spectra (in one or more electronic states), relative state populations etc., with the possibility of a multilayer formulation. We have validated the code on the diabatic surfaces recently published by Truhlar and coworkers to study the nonadiabatic photodynamics of phenol. Using an Ehrenfest-like, single-nuclear-configuration (but in a fully quantum formalism) model we calculate the optical spectrum and relative state populations of the system as a function of time.

A new Gaussian MCTDH program: implementation and validation on the levels of the water and glycine molecules.

We report the main features of a new general implementation of the Gaussian Multi-Configuration Time-Dependent Hartree model. The code allows effective computations of time-dependent phenomena, including calculation of vibronic spectra (in one or more electronic states), relative state populations, etc. Moreover, by expressing the Dirac-Frenkel variational principle in terms of an effective Hamiltonian, we are able to provide a new reliable estimate of the representation error. After validating the code on simple one-dimensional systems, we analyze the harmonic and anharmonic vibrational spectra of water and glycine showing that reliable and converged energy levels can be obtained with reasonable computing resources. The data obtained on water and glycine are compared with results of previous calculations using the vibrational second-order perturbation theory method. Additional features and perspectives are also shortly discussed.

Quantum stereodynamics for the two product channels of the F + HD reaction from the complete scattering matrix in the stereodirected representation.

For the two exit arrangements of the F + HD reaction, the full scattering matrix is obtained by exact quantum dynamics on an accurate potential energy surface. The S matrix is expressed in the stereodirected representation, for the first time, for all channels of a triatomic reaction. We analyze a collision energy where the dominant reaction mechanism is direct and a total angular momentum J = 0. It is found that the introduction of steric quantum numbers (correlated in the vector model to the angles measuring directions of approaching reactants and of separating products) provides a sharp description of stereodynamical features for both exit channels.

The shape of the potential energy surface and the thermal rate coefficients of the N + N2 reaction.

Full-dimensional quantum time-dependent calculations of the detailed probabilities of the N + N2 reaction have been performed on different potential energy surfaces, initial quantum states, and total angular momentum quantum numbers. The calculations allowed a rationalization of the effect of both moving the saddle to reaction out of collinearity and lowering its height. On some of these surfaces, more extended studies of the reactive dynamics of the system were performed. On one of them also, thermal rate coefficients were computed using J = 0 quantum probabilities and the J-shift model after testing the applicability of such a model against centrifugal sudden results. A comparison of the calculated thermal rate coefficients with theoretical and experimental data available from the literature is also made, and possible effects of inserting an intermediate well at the top of the saddle are argued.

Differential cross sections from quantum calculations on coupled Ab initio potential energy surfaces and scattering experiments for Cl(2P)+H2 reactions.

To assess the relative reactivity of the spin-orbit excited state of atomic Cl with molecular hydrogen, we have measured differential cross sections using an atomic Cl beam with a known concentration of the ground and excited spin-orbit states. These are compared with the first determination of the cross sections from quantum mechanical scattering calculations on a set of coupled ab initio potential energy surfaces. The comparison suggests that these surfaces may underestimate the degree of rotational excitation of the HCl products and that the excited spin-orbit state plays a minor role in the reaction.

Resonance-mediated chemical reaction: F+HD-->HF+D

Conclusive evidence is presented for the existence of a reactive resonance in the F+HD reaction. In a molecular beam experiment, the resonance appears in the integral cross section as a distinct steplike feature, while in the differential cross section it is manifested as sharply varying forward-backward peaks in the product distribution. A detailed analysis of the quantum dynamics establishes that a reactive resonance localized in the transition-state region is responsible for these remarkable observations. At collision energies below 1 kcal/mol, the reaction proceeds almost exclusively through resonant tunneling with very little contribution from the more conventional direct mechanism.

van der waals interactions in the Cl + HD reaction

The van der Waals forces in the entrance valley of the Cl + HD reaction are shown here to play a decisive role in the reaction's dynamics. Exact quantum mechanical calculations of reactive scattering on a potential energy surface without Cl-HD van der Waals forces predict that the HCl and DCl products will be produced almost equally, whereas the same calculations on a new ab initio potential energy surface with van der Waals forces show a strong preference for the production of DCl. This preference is also seen in crossed molecular beam experiments on the reaction. The study of chemical reaction dynamics has now advanced to the stage where even comparatively weak van der Waals interactions can no longer be neglected in calculations of the potential energy surfaces of chemical reactions.