Institut für Physikalische Chemie und Theoretische Chemie
Refine
Has Fulltext
- no (243)
Year of publication
Document Type
- Article (152)
- Doctoral Thesis (76)
- Monograph/Edited Volume (14)
- Other (1)
Is part of the Bibliography
- yes (243)
Institute
Complete 3D potential energy surfaces for the two lowest electronic states of the system (N2H)+
(1996)
Self-assembly, ordered nanostructures and functionality of polyelectrolyte-amphiphile complexes
(2000)
Photochemical and photophysical properties were investigated for poly(arylenevinylene)s containing a flexible biphenyl "hinge" unit by applying one-photon (OP) and two-photon (TP) excitation to explore excited-state properties. The poly(arylenevinylene)s were poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(4,4'-dihexyloxy-3,3'-biph enylenevinylene)] (1), poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(2,2'-dihexyloxy-3,3'-biph enylenevinylene)] (2), and poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(2,2'-biphenylene-vinylene )] (3). Effective emission quantum yields and related photonic properties were evaluated on a realistic per-chromophore basis using effective conjugation lengths based on the Strickler-Berg relationship. intramolecular photocyclization was deduced to occur in the one case where the biphenyl molecular connectivity permitted the reaction, based on matrix- assisted loser desorption/ionization time-of-flight (MALDI-TOF), heteronuclear multiple-quantum coherence (HMQC)-NMR, and gel-permeation chromatography (GPC) results. The various photoprocesses could be induced by either OP or TP excitation, though the first excited singlet state is the photoactive state. The higher excitation energy 1 of the TP excited state favors indirect population of the S, state by electronic coupling between the TP and OP excited states [lambda(max)(TPE) (nm): 726; delta (GM)([9]): 1 = 229, 2 = 215, 3 = 109). Photochemical processes occurring from the lowest OP excited state (S-1) could therefore also be indirectly induced by TP excitation
Rapeseed proteins
(1994)
Improvement of catalytic properties of SAPO-31 molecular sieves by using an activated form of SiO2
(1994)
Proteinsekundärstrukturen an der fluiden Grenzfläche - in situ - Untersuchungen mit der IRRAS
(1999)
Diffuse reflectance measurements and photon migration studies with near infrared (NIR) diode lasers were employed to elucidate experimental methods for determining absorption and scattering coefficients and species concentrations in highly scattering solutions. Applicability of theoretical approaches were established by investigating model systems with absorbing (e.g. ink, malachite green) and scattering (e.g. milk powder, caolinit) species in aqueous solution. While diffuse reflectance measurements practically requires calibration procedures, photon migration studies allow quantitative determination of absorption and scattering coefficients of turbid solutions consistent with absorptions coefficients obtained from Lambert-Beer's law. Furthermore, NIR absorption spectra of water, chlorinated hydrocarbons (chloroform, 1,2-dichloroethane, trichloroethene) and of various sugars ($alpha$-D-glucose, sucrose, maltose) are discussed. Spectral variations of NIR water absorption with temperature and solvents are exammined. Exemplary, NIR diode laser detection of water in acetone/water mixtures is performed.
Electronic intensity and frequency modulation of diode lasers enables new perspectives for highly sensitive analytical in-situ techniques. For analyis of "heterogeneous" media, which may consist of coexisting gaseous, liquid, and solid phases and often show multiple light scattering, non-invasive techniques with outstanding performance characteristics can be developed. Analysis of photon density waves launched by intensity-modulated lasers provide an elegant way for the determination of absorption and scattering coefficients of multiple scattering media. The absorption coefficient can be used for qualitative and quantitative analysis of chemical constituents (which absorb in the range of the laser wavelengths). The scattering coefficient allows characterization of physical and morphological properties of the sample. In the current work, applicability of appropriate radiation transport models was investigated with simple light scattering solutions and compared with results obtained from the treatment according to the theory of Kubelka and Munk. Measurements of human blood samples are discussed. A new method for determination of water vapor partial pressure in a polyurethane foam with a frequency-modulated external cavity diode laser is discussed.
A weak-mode representation of floppy molecules. III : theoretical assignment of spectroscopic states
(1994)
The geometric structure and bonding properties of medium-sized ArnH+ clusters (n = 2-35), in which a proton is wrapped up in a number of Ar atoms, are investigated by applying a diatomics-in-molecules (DIM) model with ab-initio input data generated by means of multi-reference configuration-interaction (MRCI) computations. For the smaller complexes, n = 2-7, cross-checking calculations employing the coupled-cluster approach (CCSD) with the same one-electron atomic basis set as for the input data calculations (aug-cc-pVTZ from Dunning), show good agreement thus justifying the extension of the DIM study to larger n. Local minima of the multi-dimensional potential-energy surfaces (PES) are determined by combining a Monte-Carlo sampling followed, for each generated point, by a steepest-descent optimization procedure. For the electronic ground state of the ArnH+ clusters, the global minimum (corresponding to the most stable structure of the cluster) as well as secondary minima are found and analyzed. The structural and energetic data obtained reveal the building-up regularities for the most stable structures and make it possible to formulate a simple increment scheme. The low-lying excited states are also calculated by the DIM approach; they all turn out to be globally repulsive
Synthese und Charakterisierung monomolekularer dicker Polyisobutenfilme mit ionischen Ankergruppen
(1999)
We report theoretical investigations on the second photoelectron band of chlorine dioxide molecule by ab initio quantum dynamical methods. This band exhibits a highly complex structure and represents a composite portrait of five excited energetically close-lying electronic states of ClO2+. Much of this complexity is likely to be arising due to strong vibronic interactions among these electronic states - which we address and examine herein. The near equilibrium MRCI potential energy surfaces (PESs) of these five cationic states reported by Peterson and Werner [J. Chem. Phys. 99 (1993) 302] for the C2v configuration, are extended for the Cs geometry assuming a harmonic vibration along the asymmetric stretching mode. The strength of the vibronic coupling parameters of the Hamiltonian are calculated by ab initio CASSCF-MRCI method and conical intersections of the PESs are established. The diabatic Hamiltonian matrix is constructed within a linear vibronic coupling scheme and the resulting PESs are employed in the nuclear dynamical simulations, carried out with the aid of a time-dependent wave packet approach. Companion calculations are performed for transitions to the uncoupled electronic states in order to reveal explicitly the impact of the nonadiabatic coupling on the photoelectron dynamics. The theoretical findings are in good accord with the experimental observations. The femtosecond nonradiative decay dynamics of ClO2+ excited electronic states mediated by conical intersections is also examined and discussed.