On the stability of the bcc phase in Cu-Al-Mn shape memory alloys

Measurements of the entropy change at the martensitic transition of two composition-related sets of Cu-Al-Mn shape-memory alloys are reported. It is found that most of the entropy change has a vibrational origin, and depends only on the particular close-packed structure of the low-temperature phase. Using data from the literature for other Cu-based alloys, this result is shown to be general. In addition, it is shown that the martensitic structure changes from 18R to 2H when the ratio of conduction electrons per atom reaches the same value as the eutectoid point in the equilibrium phase diagram. This finding indicates that the structure of the metastable low-temperature phase is reminiscent of the equilibrium structure.

Premartensitic and martensitic phase transitions in ferromagnetic Ni2MnGa

We present an experimental study of the premartensitic and martensitic phase transitions in a Ni2MnGa single crystal by using ultrasonic techniques. The effect of applied magnetic field and uniaxial compressive stress has been investigated. It has been found that they substantially modify the elastic and magnetic behavior of the alloy. These experimental findings are a consequence of magnetoelastic effects. The measured magnetic and vibrational behavior agrees with the predictions of a recently proposed Landau-type model [A. Planes et al., Phys. Rev. Lett. 79, 3926 (1997)] that incorporates a magnetoelastic coupling as a key ingredient.

Far-infrared spectroscopy of nanoscopic InAs rings

We have employed time-dependent local-spin-density theory to analyze the far-infrared transmission spectrum of InAs self-assembled nanoscopic rings recently reported [A. Lorke et al., Phys. Rev. Lett. (to be published)]. The overall agreement between theory and experiment is fairly good, which on the one hand confirms that the experimental peaks indeed reflect the ringlike structure of the sample, and on the other hand, asseses the suitability of the theoretical method to describe such nanostructures. The addition energies of one- and two-electron rings are also reported and compared with the corresponding capacitance spectra

Measurement and simulation of anisotropy in the Infrared and Raman spectra of beta-FeSi2 single crystals

In this paper we show that the orthorhombic phase of FeSi2 (stable at room temperature) displays a sizable anisotropy in the infrared spectra, with minor effects in the Raman data too. This fact is not trivial at all, since the crystal structure corresponds to a moderate distortion of the fluorite symmetry. Our analysis is carried out on small single crystals grown by flux transport, through polarization-resolved far-infrared reflectivity and Raman measurements. Their interpretation has been obtained by means of the simulated spectra with tight-binding molecular dynamics.

Laser induced thermal lens and near infrared absorption studies of ch overtones in some organic compounds

Vibrational overtone spectroscopy of X-H (X=C,N,O) containing molecules is an area of recent interest. The spectroscopic studies of higher vibrational levels yield valuable informations, regarding,the molecular structure, intra- and inter-molecular interactions, radiationless transitions, intra-molecular vibrational relaxations, multiphoton excitations and chemical reactivities, which cannot be z obtained by other spectroscopic methods. This thesis presents the results of experimental investigations on the overtone spectra of some organic compounds in the liquid phase for the characterization of CH bonds. The spectra in the fifth overtone region (1fiV=6) are recorded using a dual beam thermal lens setup and the lower overtones (.AV=2-5) are recorded spectrophotometrically.The thesis is presented in six chapters.

Premartensitic and martensitic phase transition in ferromagnetic Ni2MnGa

We present an experimental study of the premartensitic and martensitic phase transitions in a Ni2MnGa single crystal by using ultrasonic techniques. The effect of applied magnetic field and uniaxial compressive stress has been investigated. It has been found that they substantially modify the elastic and magnetic behavior of the alloy. These experimental findings are a consequence of magnetoelastic effects. The measured magnetic and vibrational behavior agrees with the predictions of a recently proposed Landau-type model [A. Planes et al., Phys. Rev. Lett. 79, 3926 (1997)] that incorporates a magnetoelastic coupling as a key ingredient.

Microwave absorption and magnetization tunneling in Mn12-acetate molecular clusters

In this paper we study the effect of microwave absorption on the quantum relaxation rate of Mn12 molecular clusters. We have determined first the resonant frequencies of a microwave resonator containing a single crystal of Mn12-Acetate and measured initial isothermal magnetization curves while microwave power was put into the resonator. We have found that the tunneling rate changes one order of magnitude for certain frequencies. This suggests that the microwave shaking of the nuclear spin and molecular vibrational degrees of freedom is responsible for the huge increasing of the tunneling rate.

NIR Spectroscopic and Laser Induced Fluorescence studies of some organic molecules

Vibrational overtone spectroscopy of molecules containing X-H oscillators (X = C, N, O...) has become an effective tool for the study of molecular structure, dynamics, inter and intramolecular interactions, conformational aspects and substituent effects in aliphatic and aromatic compounds. In the present work, the author studied the NIR overtone spectra of some liquid phase organic compounds. The analysis of the CH, NH and OH overtones yielded important structural information about these systems. In an attempt to get information on electronic energy levels, we studied the pulsed Nd:YAG laser induced fluorescence spectra of certain organic compounds. The pulsed laser Raman spectra of some organic compounds are also studied. The novel high resolution technique of near infrared tunable diode laser absorption spectroscopy (TDLAS) is used to record the rotational structure of the second OH overtone spectrum of 2-propanol. The spectral features corresponding to the different molecular conformations could be identified from the high resolution spectrum. The whole work described in this thesis is divided into five chapters.

Coherent tunnelling in Cu2+- and Ag2+-doped MgO and CaO: Cu2+ explored through ab initio calculations

The observation of coherent tunnelling in Cu2+ - and Ag2+ -doped MgO and CaO:Cu2+ was a crucial discovery in the realm of the Jahn-Teller (JT) effect. The main reasons favoring this dynamic behavior are now clarified through ab initio calculations on Cu2+ - and Ag2+ -doped cubic oxides. Small JT distortions and an unexpected low anharmonicity of the eg JT mode are behind energy barriers smaller than 25 cm-1 derived through CASPT2 calculations for Cu2+ - and Ag2+ -doped MgO and CaO:Cu2+ . The low anharmonicity is shown to come from a strong vibrational coupling of MO610- units (M=Cu,Ag) to the host lattice. The average distance between the d9 impurity and ligands is found to vary significantly on passing from MgO to SrO following to a good extent the lattice parameter.

FT-IR and FT-Raman study of Nasicon type phosphates, ASnFe(PO4)3 [A=Na2, Ca, Cd]

FT-Raman and FT-IR spectra of ASnFe(PO4)3 [A=Na2, Ca, Cd] were recorded and analyzed. The bands were assigned in terms of the vibrational group frequencies of SnO6 octahedral and PO4 tetrahedral. The spectral analysis shows that the symmetry of corner shared octahedral (SnO6) and the tetrahedral (PO4) are lowered from their free ion symmetry state. The presence of Fe3+ ions disrupts the S–N–O–S–N chain in the structure. This causes distortion of SnO6 and PO4 in the structure of all the compounds. Also it is seen that there are two distinct PO4 tetrahedra of different P–O bond lengths. One of these tetrahedra is linearly distorted in all the title compounds. The PO4 frequencies and bond lengths are calculated theoretically and are in agreement with the experimental values. The presence of PO4 polyanion in the structure can reduce the redox energy and hence reduce the metal oxygen covalency strength in the structure

Temperature dependent polarized Raman spectra of nonaaqualanthanoid (Pr) single crystal

Polarized Raman spectral changes with respect to temperature were investigated for Pr(BrO3)3·9H2O single crystals. FTIR spectra of hydrated and deuterated analogues were also recorded and analysed. Temperature dependent Raman spectral variation have been explained with the help of the thermograms recorded for the crystal. Factor group analysis could propose the appearance ofBrO3 ions at sites corresponding to C3v (4) and D3h (2). Analysis of the vibrational bands at room temperature confirms a distorted C3v symmetry for the BrO3 ion in the crystal. From the vibrations of water molecules, hydrogen bonds of varying strengths have also been identified in the crystal. The appearance υ1 mode of BrO3− anion at lower wavenumber region is attributed to the attachment of hydrogen atoms to the BrO3− anion. At high temperatures, structural rearrangement is taking place for bothH2Omolecule and BrO3 ions leading to the loss ofwater molecules and structural reorientation of bromate ions causing phase transition of the crystal at the temperature of 447 K.

A computer-algebraic approach to the study of the symmetry properties of molecules and clusters

This thesis work is dedicated to use the computer-algebraic approach for dealing with the group symmetries and studying the symmetry properties of molecules and clusters. The Maple package Bethe, created to extract and manipulate the group-theoretical data and to simplify some of the symmetry applications, is introduced. First of all the advantages of using Bethe to generate the group theoretical data are demonstrated. In the current version, the data of 72 frequently applied point groups can be used, together with the data for all of the corresponding double groups. The emphasize of this work is placed to the applications of this package in physics of molecules and clusters. Apart from the analysis of the spectral activity of molecules with point-group symmetry, it is demonstrated how Bethe can be used to understand the field splitting in crystals or to construct the corresponding wave functions. Several examples are worked out to display (some of) the present features of the Bethe program. While we cannot show all the details explicitly, these examples certainly demonstrate the great potential in applying computer algebraic techniques to study the symmetry properties of molecules and clusters. A special attention is placed in this thesis work on the flexibility of the Bethe package, which makes it possible to implement another applications of symmetry. This implementation is very reasonable, because some of the most complicated steps of the possible future applications are already realized within the Bethe. For instance, the vibrational coordinates in terms of the internal displacement vectors for the Wilson's method and the same coordinates in terms of cartesian displacement vectors as well as the Clebsch-Gordan coefficients for the Jahn-Teller problem are generated in the present version of the program. For the Jahn-Teller problem, moreover, use of the computer-algebraic tool seems to be even inevitable, because this problem demands an analytical access to the adiabatic potential and, therefore, can not be realized by the numerical algorithm. However, the ability of the Bethe package is not exhausted by applications, mentioned in this thesis work. There are various directions in which the Bethe program could be developed in the future. Apart from (i) studying of the magnetic properties of materials and (ii) optical transitions, interest can be pointed out for (iii) the vibronic spectroscopy, and many others. Implementation of these applications into the package can make Bethe a much more powerful tool.

Intrinsic channel closing in strong-field single ionization of H2

Die Ionisation von H2 in intensiven Laserpulsen wird mit Hilfe der numerischen Integration der zeitabhängigen Schrödingergleichung für ein Einelektronenmodell untersucht, das die Vibrationsbewegung berücksichtigt. Die Spektren der kinetischen Elektronenenergie hängen stark von der Vibrationsquantenzahl des erzeugten H2+ Ions ab. Für bestimmte Vibrationszustände ist die Ausbeute der Elektronen in der Mitte des Plateaus stark erhöht. Der Effekt wird "channel closings" zugeschrieben, die in Atomen durch Variation der Laserintensität beobachtet wurden. The ionization of H2 in intense laser pulses is studied by numerical integration of the time-dependent Schrödinger equation for a single-active-electron model including the vibrational motion. The electron kinetic energy spectra in high-order above-threshold ionization are strongly dependent on the vibrational quantum number of the created H2+ ion. For certain vibrational states, the electron yield in the mid-plateau region is strongly enhanced. The effect is attributed to channel closings, which were previously observed in atoms by varying the laser intensity.

Effect of dressing on high-order harmonic generation in vibrating H2 molecules

Wir entwickeln die Starkfeldnäherung für die Erzeugung hoher Harmonischer in Wasserstoffmolekülen, wobei die Vibrationsbewegung berücksichtigt wird, sowie die laserinduzierte Kopplung zwischen den beiden untersten Born-Oppenheimer-Zuständen im Molekülion, das durch die anfängliche Ionisation des Moleküls erzeugt wird. Wir zeigen, dass die Kopplung bei längeren Laserwellenlängen (≈ 2 μm) wichtig wird und zu einer Reduzierung der Erzeugung von Harmonischen führt, sowie zu einer Änderung des Verhältnisses von Harmonischen in verschiedenen Isotopen. ----------------------------------------------------------------------- We develop the strong-field approximation for high-order harmonic generation in hydrogen molecules, including the vibrational motion and the laser-induced coupling of the lowest two Born-Oppenheimer states in the molecular ion that is created by the initial ionization of the molecule. We show that the field dressing becomes important at long laser wavelengths (≈ 2 μm), leading to an overall reduction of harmonic generation and modifying the ratio of harmonic signals from different isotopes.