Implementation of dynamical nucleation theory with quantum potentials

A method is implemented within the context of dynamical nucleation theory in order to efficiently determine the ab initio water dimer evaporation rate constant. The drive for increased efficiency in a Monte Carlo methodology is established by the need to use relatively expensive quantum mechanical interaction potentials. A discussion is presented illustrating the theory, algorithm, and implementation of this method to the water dimer. Hartree–Fock and second order Møller–Plesset perturbation theories along with the Dang–Chang polarizable classical potential are utilized to determine the ab initio water dimer evaporation rate constant. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009     

Concerted reductive coupling of an alkyl chloride at Pt(IV)

Oxidation of a doubly cyclometallated platinum(II) complex results in two isomeric platinum(IV) complexes. Whereas the trans isomer is robust, being manipulable in air at room temperature, the cis isomer decomposes at -20 °C and above. Reductive coupling of an alkyl chloride at the cis isomer gives a new species which can be reoxidised. The independence of this coupling on additional halide rules out the reverse of an S(N)2 reaction, leaving a concerted process as the only sensible reaction pathway.     

Platinum(IV) centres with agostic interactions from either sp² or sp³ C-H bonds

Agostic complexes of platinum(IV) have been isolated and characterised. A Pt(II) sp3 agostic complex maintains the agostic interaction upon oxidation giving a Pt(IV) sp3 agostic complex; in another Pt(IV) complex the agostic interaction from an sp2 C-H bond is sufficient to displace another ligand.     

Emission spectra,decay times,and polarization ratios of ruthenium(II) complexes containing tridentate ligands

Luminescence from complexes of the general formula Ru(N-N-N)₂²⁺ (N-N-N = tridentate N-heterocyclic ligand) was investigated in the range of 77-2 K. Inversion of the sign of the polarization ratio occurred below 15 K. Results arr interpreted in terms of a thermally equilibrated multiple-state model for the excited manifold.     

Investigation of the temperature dependence of ruthenocene photoluminescence

Computer analysis of the luminescence decay times of ruthenocene in the range of 4.2 to 77 K has yielded energies and decay parameters for the lowest excited states. The derived level pattern has been rationalized on the basis of a ³E₁ (dd) term, split by ≈ 500 cm^-1 by spin-orbit coupling into A₂ + A₁ + E₁ + E₂ components in order of increasing energy. From a preliminary Franck-Condon analysis of the well-structured luminescence observed at 4.2 K, the molecule is shown to be expanded in the excited A₂ state, primarily along the principal symmetry axis.