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ABSTRACT: Time-resolved diffuse X-ray scattering is one powerful method for monitoring the progression from the creation of local structural changes inside a crystalline material up to the transformation of the whole crystalline bulk. In this work, we study the mechanism of phototransformation of a molecular crystal by time-resolved diffuse X-ray scattering. Here, an optical excitation source, like a pulsed laser, initiates structural transformations which are monitored by X-ray scattering techniques. We have studied the dimerization process of the molecular switch α-styrylpyrylium (trifluoromethanesulfonate) TFMS, in particular for understanding whether cooperative effects influence the changes of the structure in the bulk and its periodicity. Upon illumination with optical light, α-styrylpyrylium TFMS instantaneously photoswitches. Depending on the optical fluence, X-ray diffuse planes are observed prior to phototransformation of the bulk. In the early stages of transformation, the analysis reveals systems of randomly distributed islands of product clusters with gradual growth in size and amount. The degree of transformation follows the optical excitation profile, i.e., the spatial absorption of the laser beam. In the present studies, no influence of cooperativity on the photodimerization process has been found.
The Journal of Physical Chemistry B 08/2012; 116(36):10996-1003. · 3.70 Impact Factor
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ABSTRACT: We compare results from single crystal X-ray diffraction and FTIR spectroscopy to elucidate the nature of hydrogen bonding in β-9-anthracene carboxylic acid (β-9AC, C(15)H(10)O(2)). The crystallographic studies indicate a disorder for the protons in the cyclic hydrogen bond. This disorder allows the determination of the energy difference between two proton sites along the hydrogen bond. The temperature dependent Fourier transform infrared spectroscopy (FTIR) underpins the crystallographic results. The combination of both methods allows the estimation of a one-dimensional potential curve describing the OH-stretching motion. The dynamical properties of the proton transfer along the hydrogen bond are extracted from this potential. The work presented here has profound implication on future studies of photochemical dynamics of crystalline β-9AC, which can deliver a deeper understanding of the mechanism of photochemical driven molecular machines and the optical and electronic properties of molecular organic semiconductors.
Physical Chemistry Chemical Physics 06/2012; 14(29):10187-95. · 3.57 Impact Factor
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ABSTRACT: In this work, the Coulomb explosion of the octamer water cluster has been studied employing a theoretical approach. Instead of the usual methodology that makes use of classical molecular dynamics, time-dependent density functional theory has been applied to tackle the problem. This method explicitly accounts for the laser field and thus does not impose any constraint on the interaction between the laser pulse and the cluster. We focus on the effects of energetic changes in the system under high-intensity soft X-ray laser pulses. The motions of the ions and their velocities during this process show significant differences for the three applied laser intensities (10(14), 10(15) and 10(16) W cm(-2)). Very strong soft X-ray free electron laser (FEL) pulses must be short to allow for investigations of ultra-fast wet chemistry, according to the principle of collect and destroy.
Physical Chemistry Chemical Physics 06/2012; 14(27):9606-14. · 3.57 Impact Factor
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Henning O Sørensen,
Søren Schmidt,
Jonathan P Wright,
Gavin BM Vaughan, Simone Techert,
Elspeth F Garman,
Jette Oddershede,
Jav Davaasambuu,
Karthik S Paithankar,
Carsten Gundlach,
others
Zeitschrift für Kristallographie. 01/2012; 227(1):63-78.
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ABSTRACT: The enhancement of the x-ray scattering signal from partially aligned molecular samples is investigated. The alignment properties of the studied molecular system are modeled based on the method of laser alignment. With the advances in the area of laser alignment of molecules, the application of this sample manipulation technique promises a great potential for x-ray scattering measurements. Preferential alignment of molecules in an otherwise amorphous sample leads to constructive interference and thus increases the scattering intensity. This enhances the structural information encoded in the scattering images and enables improved resolution in studies of reaction dynamics, as in this work is shown for the example of the photo-isomerization of stilbene. We demonstrate that the scattering signal is strongly influenced by the alignment axis. Even the most basic one-dimensional alignment offers significant improvement compared to the structural information provided by a randomly oriented sample. Although the signal is sensitive to the uncertainty in the alignment angle, it offers encouraging results even at realistic alignment uncertainties.
The Journal of chemical physics 02/2011; 134(5):054302. · 3.09 Impact Factor
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ABSTRACT: A manifold of ordering transitions relevant to chemical and biological systems occur at interfaces from liquids to self-assembled soft solids like membranes or liquid crystals. In the present case, we were interested in understanding the phase transition from the microemulsion phase to the liquid crystal phase in terms of their driving forces, i.e., activation energy and entropy. The purpose of this work was to clarify the influence of concentration effects of the amphiphilic molecules on the nature of these self-assembly processes. By photosensitization of the model system (polyalkylglycolether (C(10)E(4)), water, decane, and cyclohexane) with laser dyes, we could effectively induce and control the phase transition through the absorption of optical photons. The photo transformation conditions were chosen in such a way that the system was in thermal equilibrium. By application of time-resolved photo small-angle X-ray scattering we could monitor the conversion process and demonstrate that the surfactant concentration has a direct impact on the activation energy, which is observable through the length of the induction time.
The Journal of Physical Chemistry A 02/2011; 115(11):2176-83. · 2.95 Impact Factor
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ABSTRACT: We computationally examine various aspects of the reaction dynamics of the photodissociation and recombination of molecular iodine. We use our recently proposed formalism to calculate time-dependent x-ray scattering signal changes from first principles. Different aspects of the dynamics of this prototypical reaction are studied, such as coherent and noncoherent processes, features of structural relaxation that are periodic in time versus nonperiodic dissociative processes, as well as small electron density changes caused by electronic excitation, all with respect to x-ray scattering. We can demonstrate that wide-angle x-ray scattering offers a possibility to study the changes in electron densities in nonperiodic systems, which render it a suitable technique for the investigation of chemical reactions from a structural dynamics point of view.
The Journal of chemical physics 09/2010; 133(12):124309. · 3.09 Impact Factor
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ABSTRACT: Time-resolved Laue crystallography has been employed to study the structural dynamics of a one-dimensional organic conductor (tetrathiafulvalene-p-chloranil) during photoexcitation in the regime of the neutral to ionic phase transition. Exciting this crystalline system with 800 nm 100 fs long optical pulses leads to ultrafast population of a structural intermediate as early as 50 ps after excitation with a lifetime of at least 10 ns. Starting from the neutral phase, this intermediate has been assigned as a precursor state toward the photoinduced population of the ionic phase. The observed intensity changes are significantly different from comparable equilibrium structures. The interpretation of this structural data is that the potential of this intermediate is being softened during its population in a dynamical process. The depopulation proceeds through thermal processes.
The Journal of Physical Chemistry A 07/2010; 114(29):7677-81. · 2.95 Impact Factor
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ABSTRACT: Home-based soft X-ray time-resolved diffraction (TR-SXD) experiments with nanosecond time resolution (10 ns) and nanometer spatial resolution were carried out at a tabletop soft X-ray plasma source (2.7-5.9 nm). The investigated system was the lyotropic liquid crystal C(16)E(7)/paraffin/glycerol/formamide/IR 5. Usually, major changes in physical, chemical, and/or optical properties of the sample result from structural changes and shrinking morphology. Here, these effects occur as a consequence of the energy absorption in the sample upon optical laser excitation in the IR regime. The variations observed are integral intensity modulations and displacement in the Bragg diffraction angle. To follow the diffracted integral intensity changes, Patterson analysis was used, and the lattice parameter d variations have been followed by applying the Bragg diffraction law. The experimental intensity modulations occur on the nanosecond time scale, and they are assigned to photoinduced diffusion processes within the liquid crystalline phase. The structural response after photoexcitation is experimentally observed as an increase of the lattice constant by 0.5-1 A and is interpreted as a decrease of order in the liquid crystalline phase. This coincides with a reorientation to a photocreated liquid crystal lattice in the surface plane and with respect to the E-field vector of the laser light. The present studies emphasize the possibility of using TR-SXD techniques for studying the transient mechanical dynamics of nanosystems at the submicrosecond time scale.
The Journal of Physical Chemistry B 07/2010; 114(26):8593-9. · 3.70 Impact Factor
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ABSTRACT: Home-based soft X-ray time-resolved scattering experiments with nanosecond time resolution (10 ns) and nanometer spatial resolution were carried out at a table top soft X-ray plasma source (2.2-5.2 nm). The investigated system was the lyotropic liquid crystal C(16)E(7)/paraffin/glycerol/formamide/IR 5. Usually, major changes in physical, chemical, and/or optical properties of the sample occur as a result of structural changes and shrinking morphology. Here, these effects occur as a consequence of the energy absorption in the sample upon optical laser excitation in the IR regime. The liquid crystal shows changes in the structural response within few hundred nanoseconds showing a time decay of 182 ns. A decrease of the Bragg peak diffracted intensity of 30% and a coherent macroscopic movement of the Bragg reflection are found as a response to the optical pump. The Bragg reflection movement is established to be isotropic and diffusion controlled (1 micros). Structural processes are analyzed in the Patterson analysis framework of the time-varying diffraction peaks revealing that the inter-lamellar distance increases by 2.7 A resulting in an elongation of the coherently expanding lamella crystallite. The present studies emphasize the possibility of applying TR-SXRD techniques for studying the mechanical dynamics of nanosystems.
International Journal of Molecular Sciences 11/2009; 10(11):4754-71. · 2.60 Impact Factor
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ABSTRACT: The ultrafast structural dynamics of the [2+2] photocycloaddition of alpha-styrylpyrylium trifluoromethanesulfonate (TFMS) has been studied in great detail. During the photoreaction, optical and infrared spectroscopy confirms that crystals of alpha-styrylpyrylium change color. Since the reaction is reversible, it has been suggested to be used as an organic holographic storage device. The present photocrystallographic studies (with high spatial resolution) allow for an electron density analysis of the overall reaction kinetics, revealing the mechanism of bond-breaking and bond-formation. It could furthermore be proved how the reaction is influenced by the rearrangement of the surrounding moieties. Picosecond time-resolved X-ray diffraction studies allow for the monitoring the photoreaction in crystalline thin films under experimental conditions where the transformation times are greatly enhanced. These investigations are discussed in the context of the photocrystallographic results. It has been found that alpha-styrylpyrylium TFMS undergoes an ultrafast photoreaction to the dimer product state and back-reaction to the monomer reactant state which is temperature driven. The present experiments indicate that TFMS reacts on time scales which are the fundamental limiting ones of two-quantum systems and therefore has the potential to be used as an ultrafast organic molecular switcher.
Journal of the American Chemical Society 10/2009; 131(41):15018-25. · 9.91 Impact Factor
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ABSTRACT: According to their phase diagram, polyalkyl glycol ether dissolved in ternary solutions (water, alcane, and cyclohexane) lead to the formation of either liquid crystal phases or microemulsion phases. By photosensitization of the ternary system with laser dyes and choosing the adequate concentration and temperature conditions of these lyotropic systems, it is possible to photoinduce the phase transitions from the microemulsion phase to the liquid crystal phase (and vice versa). The phototransformation conditions were chosen in such a way that the system is in thermal equilibrium during the entire phase transition. The method of photo small angle x-ray scattering has been applied to investigate the mechanism of photoinduced phase transition. Spectroscopically, the mechanism of photoinduced phase transition has been characterized by optical absorption and emission techniques.
The Journal of chemical physics 08/2008; 129(2):024502. · 3.09 Impact Factor
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ABSTRACT: In this work we present a general theoretical outline for calculating time-dependent x-ray scattering signal changes from first principles. We derive a formalism for the description of atom-atom correlation functions as Fourier transforms of quantum-chemically calculated electron densities and show their proportionality to the molecular form factor. The formalism derived in this work is applied to the photoisomerization of stilbene. We can demonstrate that wide-angle x-ray scattering offers a possibility to study the changes in electron densities in nonperiodic complex systems, which renders it a suitable technique for the investigation of (bio)organic systems.
The Journal of Chemical Physics 01/2007; 125(22):224101. · 3.33 Impact Factor
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ABSTRACT: We have studied the catalytic efficiency of acetylcholinesterase (AChE) in various solutions with ion-disturbed water structure to explore the role that the water structure plays in the substrate-enzyme encounter. The extent of water structuring in the different aqueous solutions was determined by near-infrared spectroscopy. The influence of water structure on the degree of solvation and on the intramolecular mobility of AChE was investigated for different aqueous ionic solutions by small-angle x-ray scattering technique and depolarization fluorescence spectroscopy. It was found that the encounter process between AChE and acetylthiocholine was promoted in solutions with less structured water. In these solutions it was also found that AChE is less solvated coinciding with higher intramolecular mobility. The found experimental results suggest that the water structure may influence the substrate-enzyme encounter process by diminishing the AChE solvation shell and may help diffusion of the substrate through the gorge by enhancing the intramolecular mobility of AChE.
Biophysical Journal 10/2005; 89(3):1990-2003. · 3.65 Impact Factor
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ABSTRACT: Laser- and light-induced charge density variations in organic molecular single crystals of 2-benzyl-5-benzylidene-cyclopentanone (BBCP) have been investigated using high resolution x-ray diffraction and spectroscopic methods.In BBCP single crystals a cyclobutane ring is formed from two parallel double bonds of neighbouring molecules by light irradiation. Due to this photodimerization, the bond lengths, bond angles and electron density are strongly changed near the C = C double bonds in the molecules, as has been shown by spectroscopic techniques and diffraction methods.Also, the overall transformation of the crystals from the reactant to the product state via a transient structure with a picosecond lifetime has been found by time-resolved x-ray diffraction, and by the time-correlated single-photon counting measurements.
Journal of Physics D Applied Physics 05/2005; 38(10A):A204. · 2.54 Impact Factor
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ABSTRACT: The molecular structure of photoexcited crystalline 4-(diisopropylamino)benzonitrile (DIABN) is determined by time-resolved X-ray diffraction with a time resolution of 70 ps. Spectroscopic results suggest that an ICT state with a lifetime of 3 ns is produced after photoexcitation. According to structural refinement of the X-ray data (powder diffraction), the torsional angle of the diisopropylamino group with respect to the plane of the phenyl ring of DIABN decreases from 14 degrees in the electronic ground state to 10 degrees in the equilibrated ICT state.
Journal of the American Chemical Society 06/2004; 126(17):5593-600. · 9.91 Impact Factor
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Eric Collet,
Marie-Hélene Lemée-Cailleau,
Marylise Buron-Le Cointe,
Hervé Cailleau,
Michael Wulff,
Tadeusz Luty,
Shin-Ya Koshihara,
Mathias Meyer,
Loic Toupet,
Philippe Rabiller, Simone Techert
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ABSTRACT: We report the direct observation by x-ray diffraction of a photoinduced paraelectric-to-ferroelectric structural phase transition using monochromatic 100-picosecond synchrotron pulses. It occurs in tetrathiafulvalene-p-chloranil, a charge-transfer molecular material in which electronic and structural changes are strongly coupled. An optical 300-femtosecond laser pulse switches the material from a neutral to an ionic state on a 500-picosecond time scale and, by virtue of intrinsic cooperativity, generates self-organized long-range structural order. The x-ray data indicate a macroscopic ferroelectric reorganization after the laser irradiation. Refinement of the structures before and after laser irradiation indicates structural changes at the molecular level.
Science 05/2003; 300(5619):612-5. · 31.20 Impact Factor
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ABSTRACT: Picosecond transient absorption spectroscopy and picosecond spectro-streak fluorescence measurements have been carried out in order to understand the complex photophysical dynamics of directly linked donor−acceptor systems and the solvation dynamics in longer-chain alcohols. With these techniques, the fast solvent response to optically generated charge transfer (CT) species can be followed. Studies were performed on covalently linked donor−acceptor systems of the type pyrene with derivatives of N,N-dimethylaniline: dimethyl-(4-pyren-1-yl-phenyl)-amine, dimethyl-(3-methyl-4-pyren-1-yl-phenyl)-amine and (3,5-dimethyl-4-pyren-1-yl-phenyl)-dimethylamine. The results are interpreted with particular emphasis on solvation dependent electronic restructuring of the CT species. We suggest a mechanism where the adiabatic electronic restructuring coincides with the coupling to the torsional degrees of freedom of the solvent.
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