Multipole-Bound Molecular Negative Ions

 Within the framework of a simple electrostatic model, as compared to recent experimental results, we here discuss the stability of very weakly bound molecular negative ions. In contrast with the case of conventional valence anions, the excess electron is then located in a very diffuse orbital and is mainly bound by electrostatic dipolar, quadrupolar, and polarization forces, at large distances from the neutral molecular core. By fitting a single repulsion parameter of the model to the available experimental data, it is possible to make quantitative predictions of the excess-electron binding energies in these species. Critical values of the dipole moment, quadrupole moment or polarizability required for the observation of stable multipole-bound negative ions are predicted and compared to available experimental data and ab initio calculations. Received October 24, 2001; accepted for publication November 16, 2001     

Fluorescence line narrowed spectra of Zn and metal-free cytochrome c

Fluorescence line narrowing (FLN) spectroscopy was used to study the role of the polypeptide chain in influencing the spectrum of Zn-substituted cytochrome c (Zn cyt c) and metal-free cyt c (porphyrin cyt c). For both derivatives the spectra show characteristics of relaxed fluorescence from an inhomogeneously broadened sample. Zero phonon lines and phonon wings can be clearly distinguished, and vibrational frequencies of the ground and excited states were identified. The inhomogeneous distribution width for porphyrin cyt c is slightly wider than that of Zn cyt c and a second population of molecules was apparent in the porphyrin cyt c. The phonon coupling was greater for Zn cyt c than for porphyrin cyt c, which may be due to the extra coupling to the polypeptide chain by metal ligation.This work has been done in partial fulfillment of the requirements for the Doctor of Philosophy degree.     

Thermal helium clusters at 3.2 Kelvin in classical and semiclassical simulations

The thermodynamic stability of⁴He_4–13 at 3.2 K is investigated with the classical Monte Carlo method, with the semiclassical path-integral Monte Carlo (PIMC) method, and with the semiclassical all-order many-body method. In the all-order many-body simulation the dipole-dipole approximation including short-range correction is used. The resulting stability plots are discussed and related to recent TOF experiments by Stephens and King. It is found that with classical Monte Carlo of course the characteristics of the measured mass spectrum cannot be resolved. With PIMC, switching on more and more quantum mechanics. by raising the number of virtual time steps results in more structure in the stability plot, but this did not lead to sufficient agreement with the TOF experiment. Only the all-order many-body method resolved the characteristic structures of the measured mass spectrum, including magic numbers. The result shows the influence of quantum statistics and quantum mechanics on the stability of small neutral helium clusters.     

Self-consistent treatment of the Anderson model

TheN-fold degenerate Anderson single impurity model in the infiniteU limit is treated by means of the irreducible Green functions method. In this approach a derivation of an exact Dyson equation and an exact self-energy operator is possible. The necessity of introducing auxiliary fields, such as slave-bosons is avoided.     

Growth properties of Sobolev space functions over unbounded domains

Summary We study Sobolev space functions with prescribed growth properties on large spheres. In particular, we prove a weighted Poincaré type inequality for such functions. An extension to weighted Sobolev spaces is sketched.

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Sunto Si studiano funzioni che appartengono a certi spazi di Sobolev e che hanno crescita assegnata su sfere di grande raggio. Per tali funzioni si dimostra una disuguaglianza di tipo Poincaré con peso. Si indica inoltre anche una estensione di tale risultato a funzioni in spazi di Sobolev con peso.

     

Gauge-invariant treatment of the exponential decay of an unstable atomic state

Summary By using a self-consistent projection-operator method, developed recently by the present author, a gauge-invariant Markovian treatment of the spontaneous decay of an unstable atomic state is presented. Without ignoring retardation and electron-spin effects a gauge-invariant result for the probability amplitude of finding the atom in the unstable state is obtained.