Ab initio calculations,using a small Gaussian basis set,of the electronic structure of the sulphate ion

Ab initio molecular orbital calculations of the electronic structure of the sulphate ion have been performed in which three Gaussian-type functions are used to simulate each member of a minimal basis of Slater-type orbitals. Comparative calculations on H₂S show that such a basis excellently reproduces the properties of the valence electrons given by calculations in a Slater basis. The expansion of the basis by the addition of sulphur 3d orbitals results in a large decrease in the molecular energy (1 a.u.) and has a pronounced effect on the ordering and energy of the molecular orbitals. The results of a number of semiempirical schemes are discussed in the light of these results.     

A μSR Study of Er Spin Dynamics in (Y1−x Er x )Ni2B2C Superconductors

Zero field μSR has been used to probe rare earth spin dynamics in the magnetic superconductors, Y_1−x Er _x Ni₂B₂C. The muon spin relaxation function is stretched exponential, exp (−(λt)^β), in form, as usually found for spin glass systems above the glass temperature. However, the Y_1−x Er _x Ni₂B₂C compounds show no evidence of coexisting superconducting and static spin glass ground states even at concentrations below the critical value (x=0.6) for long range antiferromagnetic order. The temperature dependence of both the muon spin relaxation rate λ and the exponent β suggests that Er spin dynamics change significantly at the superconducting transition temperature. This revised version was published online in September 2006 with corrections to the Cover Date.     

Master equation methods for multiple well systems: application to the 1-,2-pentyl system

The master equation (ME) provides a powerful technique for modeling reactions that involve at least one potential energy well. It can be widely applied to reactions with several connected energy wells and multiple product channels. The application of the technique is reviewed by reference to the H + SO(2) reaction, where phenomenological rate constants for use, for example, in a combustion model can be extracted through an analysis of the eigenvalues and eigenvectors of the collision matrix, M, that describes formation of the adducts HSO(2) and HOSO from the source H + SO(2), collisional energy transfer in the adduct wells and reaction via the product channel (sink) OH + SO. The approach is extended to systems with more than one sink and it is demonstrated that macroscopic (phenomenological) rate coefficients derived from a ME obey detailed balance if the original ME is appropriately constructed. The method has been applied to the 1-, 2-pentyl radical system, that includes isomerisation and dissociation via two channels to form C(3)H(6) + C(2)H(5) and C(2)H(4) + C(3)H(7). The calculations clearly demonstrate the importance of indirect dissociation channels, in which an isomer can dissociate to form the product set to which it is not directly connected, e.g. formation of C(3)H(6) + C(2)H(5) from 1-pentyl, via the energized states of 2-pentyl. As in previous studies of pentyl dissociation, there is a convergence of the chemically significant eigenvalues and the internal energy relaxation eigenvalues above approximately 1000 K; the consequences of this convergence are discussed.     

The calculation of the ionization energies of CrOCl3 by configuration-interaction and ΔSCF methods

The calculation of the valence ionization energies of CrOCl₃ by a configuration-interaction method is described and compared with the He(I) and He(II) photoelectron spectra of this molecule. Such a calculation yields ionization energies in good agreement with experiment and is superior to the ΔSCF method which predicts the incorrect ground state of CrOCl⁺₃.     

Low temperature CVD growth of PbS films on plastic substrates

The low temperature growth of crystalline PbS films has been achieved on plastic substrates by CVD using a xanthate. The possible mechanism involved in this low temperature deposition has been probed by density functional theory calculations.     

Unlocking the secrets of supernovae through their light curves,spectra & polarization

Utilizing the radiative transfer code cmfgen, we have undertaken time-dependent radiative transfer calculations that compute the light curve and spectra for Type Ia, Ib, Ic, and II supernovae (SNe) through the photospheric and nebular phases. The non-LTE calculations allow for a multitude of atomic processes (bound–bound, bound–free, free–free, collisional, charge exchange, and Penning ionization) and for non-thermal excitation and ionization from non-thermal electrons created by the degradation in energy of high-energy (～1 MeV) gamma-rays. The proper inclusion of all these processes requires a vast amount of atomic data. Not all the atomic data is available, and the quality of the available atomic data varies considerably. We have confirmed the results of Utrobin and Chugai (2005) that time dependent terms must be included in the statistical equilibrium equations in order to model the Hα evolution of SN 1987A, shown that time dependent terms influence other spectral features, and shown that these conclusions also apply to the modeling of Type II SNe in general. The inclusion of non-thermal processes has allowed us to model Hα and He i emission in Type II SNe into the nebular phase, and to model the He i emission in Type Ib and Ic SNe. Our calculations show that the He deficiency in Ic SNe is unlikely to be real – instead, the absence of He i on SNe Ic spectra is more likely related to inefficient excitation of He iions. Simply by varying the amount of mixing we are able to create spectra of Type Ib and Ic SNe using the SAME progenitor model. Based on a new grid of SNe Ib/c models, we confirm previous findings that the typically fast-rising narrow-peak fast-declining SNe Ib/c light curves imply ejecta masses $\mathrm{?}5{\text{M}}_{\odot }$, favoring intermediate-mass massive stars in interacting binaries. We are successfully applying cmfgen to model Type Ia SNe, and are currently exploring the role of mixing and non-thermal processes in these SNe. We highlight the differences between the various classes of SNe.     

Interpretative methods in photoelectron spectroscopy

Experimental carbon and nitrogen core electron binding energies measured by high energy photoelectron spectroscopy are reported together with ab initio and semi-empirical molecular orbital studies for a series of organic pseudohalides. The derived wavefunctions are used in a discussion of molecular potential models which are employed in the interpretation of core photoelectron spectra. The application of localized wavefunctions in this context is described.     

Core electron ionization energies and electronic structure of Ti(NO3)4 and Cu(NO3)2

Gas phase X-ray photoelectron spectra of Ti(NO₃)₄ and Cu(NO₃)₂ are reported and discussed in terms of the molecular charge distributions. No measurable splitting is observed between the 1s ionization energies of the chemically distinct oxygen atoms in either molecule. Ab initio calculations for Cu(NO₃)₂ suggest that this is due in large measure to differential orbital relaxation occurring upon core electron ionization.     

The electronic structure of dinuclear transition-metal complexes containing metal—metal interactions: II. He(I) and He(II) photoelectron spectra of hexacarbonyldi-irondisulfur and related complexes

The He(I) and He(II) photoelectron spectra of a series of Fe₂(CO)₆LL¹-type complexes (L = L¹ = S, (i-propyl)S; L,L¹ = t-but of an all-electron, ab initio SCF MO calculation on Fe₂(CO)₆S₂ and of extended CNDO calculations on related molecules. Assignments given ar He(I)/He(II) intensity differences, and on comparison with related molecules.The coordination of the bridging ligands to the metal centres and the nature of the metal—metal interactions are discussed.