Low Temperature Sol-Gel Preparation of Nanocrystalline TiO2 Thin Films

TiO₂ nanocrystalline thin films with varying degree of porosity have been prepared using a low temperature method. TiO₂ films of the anatase form have been obtained by using a polyethylene glycol (PEG) modified sol-gel method. Densification and crystallization of the films was found to result from the thermal treatment of the dip coated films in boiling water. The films have been characterized by Raman, XRD, FTIR, AFM and optical methods. Highly transparent films with transmission in excess of 85% and porosity as high as 58% are formed predominantly of anatase crystallites of dimensions of the order of 5 nm. Initial results on lithium intercalation into these films resulting in an efficient optical modulation in the visible and near infrared regions demonstrate a good potential of these films for electrochromic applications.     

Local products for relativistic quantum fields

A definition of local functions of generalized free fields is suggested. Their concrete form is determined in a fairly general setting by analysing realizations of locality. A huge class of new models of relativistic quantum fields results in this way.Presented at the International Conference Selected Topics in Quantum Field Theory and Mathematical Physics, Bechyn, Czechoslovakia, June 23–27, 1986.     

Map dependence of the fractal dimension deduced from iterations of circle maps

Every orientation preserving circle mapg with inflection points, including the maps proposed to describe the transition to chaos in phase-locking systems, gives occasion for a canonical fractal dimensionD, namely that of the associated set of for whichf =+g has irrational rotation number. We discuss how this dimension depends on the orderr of the inflection points. In particular, in the smooth case we find numerically thatD(r)=D(r ^–1)=r ^–1/8.     

A geometrical approach to bifurcation for nonlinear boundary value problems

Summary In this note we use a new averaging method, which was introduced in [2], to explain the geometrical behaviour of systems governed by nonlinear boundary value problems of the formy+g(y)=K sin(t),y(0)=y(/)=0. We show by numerical computations that global features of the solutions (such as the number of solutions, their magnitude, bifurcation behaviour, etc.) agree in both the original and averaged model. As an example, the pendulum equation is discussed in detail.

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Zusammenfassung In dieser Arbeit benutzen wir eine neue, in [2] eingeführte Mittelwertmethode, um das geometrische Verhalten nichtlinearer Randwertprobleme der Formy+g(y)=K sin(t),y(0)=y(/)=0. zu erklären. Wir belegen durch numerische Untersuchungen, daß globale Eigenschaften der Lösungen (wie z. B. die Anzahl der Lösungen, ihre Größenordnung, das Verzweigungsverhalten usw.) in der originalen und genäherten Gleichung übereinstimmen. Als Beispiel wird die Pendelgleichung ausführlich diskutiert.

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Supported by the Deutsche Forschungsgemeinschaft under grant No. BA 735/3-1     

Two-photon four-level hologram recording in poly-(alkyl-α-cyanoacrylates)

We have investigated the suitability of poly-(alkyl--cyanoacrylates) (p-(alkyl-CAc)) for two-photon four-level holographic recording. It is shown that these materials follow indeed a two-photon four-level mechanism with the second absorption step in the near infrared. Light induces the polymerization of residual monomer in the matrix. The reaction is associated with positive density changes. The sensitivity ofp-(alkyl-CAc) depends strongly on composition and age of the sample. Maximum sensitivities achieved are comparable to the so far best-known two-photon four-level ir-sensitive systems.     

Ab initio study of the NMR shielding constants and spin-spin coupling constants in cyclopropene

Summary Ab initio calculations of parameters which characterize the NMR spectrum are presented for the cyclopropene molecule. The London orbitals CHF (or GIAO-CHF, Gauge-Independent Atomic Orbital Coupled Hartree-Fock) results for the shielding constants are in good agreement with the experimental data, accurately determined, and with otherab initio values. The calculations of the NMR spin-spin coupling constants have been performed using the Multiconfiguration Time-Dependent Hartree-Fock (MC TDHF) approach. Different basis sets and MC SCF wavefunctions were used to estimate the accuracy of the results. Good agreement is obtained with the coupling constants estimated using the available experimental data.Dedicated to Professor Werner Kutzelnigg on the occasion of his 60th birthday     

The structure of liquid water. A low frequency (10–400 cm) Raman study

The recently developed molecular form of the ground state inversion potential method (GIPM) is applied here to the calculation of the total subshell photoionization cross sections of the water molecule in the energy range from threshold to 50 eV. The results show that the ionization can be accurately represented as a superposition of atomic processes.     

Two-photon absorption in quadrupolar pi-conjugated molecules: influence of the nature of the conjugated bridge and the donor-acceptor separation

Quadrupolar-type substitution of pi-conjugated chromophores with donor and acceptor groups has been shown to increase their two-photon absorption (TPA) response by up to two orders of magnitude. Here, we apply highly correlated quantum-chemical calculations to evaluate the impact of the nature of conjugated bridge and the charge-transfer distance on that enhancement. We compare chromophores with phenylenevinylene-, thienylenevinylene-, polyene-, and indenofluorene-type backbones substituted by dimethylamino and cyano groups. In all compounds, we find a strongly TPA-active A(g) state (either 2A(g) or 3A(g)) in the low-energy region, as well as a higher lying TPA-active state (mA(g)) at close to twice the energy of the lowest lying one-photon allowed state; the smaller energy detuning in the mA(g) states results in very large TPA cross sections delta. We also investigate the influence of the degree of ground-state polarization on TPA. Independent of the nature of the backbone and the donor-acceptor separation, delta displays the same qualitative evolution with a maximum before the cyanine-like limit; the highest TPA cross sections are calculated for distirylbenzene- and polyene-based systems.     

Origin of high second- and third-order nonlinear optical response in ammonio/borato diphenylpolyene zwitterions: the remarkable role of polarized aromatic groups

We present a quantum-chemical analysis of the molecular structure and second- and third-order polarizabilities in a series of promising nonlinear optical (NLO) chromophores, the zwitterionic ammonio/borato diphenylpolyenes, R3N+Ph(C=C)nPhB-R3, whose synthesis has been reported recently. The molecular geometries are obtained via MP2/6-31G optimization, while the NLO properties are calculated with the INDO Hamiltonian using the sum-over-states and finite-field real-space methods. The real-space approach allows the direct evaluation of the NLO-active segments of the molecules, while the sum-over-states results illustrate the virtual excitations and charge-transfer pathways that are essential in the NLO response. Both methods highlight the remarkable and unexpected result that it is the strongly polarized phenylene groups that play the key role in generating a high NLO response.