Proefschr. Rijksuniversiteit Groningen. / Met lit. opg.-Met samenvatting in het Nederlands en Slovaaks.

Proefschrift Rijksuniversiteit Groningen. / Auteursnaam op omslag: Jaap J.D. de Jong. Met lit.opg. - Met samenvatting in het Nederlands.

In dieser Arbeit wird Femtosekunden-Spektroskopie im mittleren Infrarot angewandt auf einige der am gründlichsten studierten fotoinduzierten Reaktionen: der Wasserstoff-Protonentransfer im elektronischen angeregten Zustand, für einen intramolekularen und einen intermolekularen Fall, sowie die Isomerisation fotochromer Verbindungen. Elektronische Spektroskopie ist die am häufigsten verwendete Methode zur Untersuchung ultraschneller Reaktionsdynamik in der kondensierten Phase, wobei Übergänge zwischen elektronischen Zuständen der reagierenden molekularen Systeme beobachtet werden. Häufig werden elektronische Übergänge abgetastet, deren Wellenfunktionen delokalisiert sind, so dass kaum ortspezifische Information erhalten wird. Außerdem ist aufgrund der breiten Absorptionslinien, die aus den schnellen Dephasierungszeiten elektronischer Übergänge resultieren, eine verlässliche Interpretation der experimentellen Daten schwierig; dies umso mehr, je komplexer der Reaktion ist, z.B. durch die Anwesenheit verschiedener Isomere oder durch das Zusammenwirken vieler elektronischer Zustände. Femtosekunden-Infrarotspektroskopie wird in dieser Arbeit als leistungsfähige Alternative eingesetzt, um ultraschnelle Reaktionsdynamik zu beobachten, und so den hohen Grad an Korrelation zwischen Infrarotspektren und molekularer Struktur sowie die Vorteile schmaler Bandbreiten IR-aktiver Schwingungsmoden auszunutzen. / In this thesis femtosecond mid-infrared spectroscopy has been applied to the investigation of some of the most thoroughly studied photoinduced reactions: the excited state hydrogen/proton transfer, both in an intramolecular and in an intermolecular case, and the isomerization of photochromic compounds. Electronic spectroscopy is the most commonly used method for ultrafast studies of molecular reaction dynamics in the condensed phase, whereby the electronic states of the reacting molecular systems are monitored. These techniques typically probe electronic transitions occurring between delocalized orbitals and - thus - do not provide site-specific information. Besides, the broad absorption lines resulting from the fast dephasing times of electronic transitions in solutions may hinder a reliable interpretation of the experimental results, especially when the complexity of the reaction increases, due e.g. to the presence of different isomers or to the involvement of numerous electronic states. Femtosecond infrared spectroscopy has been used in this work as a powerful and complementary alternative to probe ultrafast reaction dynamics, exploiting the high degree of correlation between the infrared spectra and the molecular structure and the advantages stemming from the narrow bandwidths of IR-active vibrational modes.

This diploma thesis is focused on study of electric and optoelectric properties of conjugated polymers. The theoretical part describes the relationship between molecular structure of conjugated materials and their chosen macroscopic physical properties like absorption of visible and ultraviolet radiation, electrical conductivity and photoconductivity. This part also describes photochromism and its utilization for construction of light driven current switch. The experimental part studies this switch based on change of photochromic species dipole moment dispersed in conjugated conducting polymer. The active switching unit is represented by photochromic spiropyran 1’,3’-dihydro-1’,3’,3’-trimethyl-6-nitrospiro[2H-1-benzopyran-2,2’-(2H)-indol] which is dispersed in conjugated conducting polymer poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene-vinylen]. The influence of the photochromic conversion on the polymer matrix was studied by absorption spectroscopy, current-voltage measurements and spectrally resolved steady state photoconductivity and transient photoconductivity.

The main objective of this thesis is the study of the optical and optoelectronic properties of organic semiconducting materials. At the beginning of this thesis is shown the growing interest in these materials and their practical application. The theoretical part presents the current state of knowledge of studied problematic related to optical phenomena and the transport of charge carriers in organic semiconductors, photochormic phenomena of reversible molecular switch and charge transfer in DNA biopolymeric matrix. Experimental section, which consists of selected author’s publications, includes study of the charge transport, photochromic reversible switching and the role of dopant in pi-conjugated organic polymer system. Conductive and semiconductive characteristics of the DNA biopolymer have been aslo studied. Conductive and photoconductive techniques together with measurement of the optical characteristics have been used for organic semiconductors characterization.