Dr. Sergey Kovalenko
Profil
Forschungsthemen1
Angeregte Zustände und Spontane Polarisation Effekte in Biarylischen Farbstoffen
Quelle ↗Förderer: DFG Sachbeihilfe Zeitraum: 09/2020 - 11/2021 Projektleitung: Dr. Sergey Kovalenko
Mögliche Industrie-Partner10
Stand: 26.4.2026, 19:48:44 (Top-K=20, Min-Cosine=0.4)
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Publikationen25
Top 25 nach Zitationen — Quelle: OpenAlex (BAAI/bge-m3 embedded für Matching).
Physical Review A · 495 Zitationen · DOI
Pump--supercontinuum-probe (PSCP) spectroscopy with femtosecond time resolution is developed theoretically and experimentally. The connection to previous theoretical results on nonchirped probing is established. It is experimentally shown that the supercontinuum can be described as a single chirped pulse. A key problem of the technique---the precise time correction of transient spectra---is solved by monitoring the nonresonant electronic response from a pure solvent (liquids) or from a transparent substrate (solid films). This allows for an adequate characterization of the supercontinuum, in particular, for directly measuring the spectral dependence of the pump-probe cross correlation. For 50-fs pump pulses, a theoretical estimate gives an accuracy for the time correction of 10 fs, which is typically \ensuremath{\approx}1/30 of the supercontinuum pulse duration. Hence a time resolution of 10--20 fs can be experimentally realized. Contributions to the nonresonant transient signal from high-frequency Raman excitations and from low-frequency impulsive-stimulated Raman processes are discussed. The PSCP technique is illustrated by results from experiments with fused silica and several common solvents and with a chromophore in solution.
Chemistry - A European Journal · 408 Zitationen · DOI
Improving the photochemical properties of molecular photoswitches is crucial for the development of light-responsive systems in materials and life sciences. ortho-Fluoroazobenzenes are a new class of rationally designed photochromic azo compounds with optimized properties, such as the ability to isomerize with visible light only, high photoconversions, and unprecedented robust bistable character. Introducing σ-electron-withdrawing F atoms ortho to the NN unit leads to both an effective separation of the n→π* bands of the E and Z isomers, thus offering the possibility of using these two transitions for selectively inducing E/Z isomerizations, and greatly enhanced thermal stability of the Z isomers. Additional para-electron-withdrawing groups (EWGs) work in concert with ortho-F atoms, giving rise to enhanced separation of the n→π* transitions. A comprehensive study of the effect of substitution on the key photochemical properties of ortho-fluoroazobenzenes is reported herein. In particular, the position, number, and nature of the EWGs have been varied, and the visible light photoconversions, quantum yields of isomerization, and thermal stabilities have been measured and rationalized by DFT calculations.
The Journal of Chemical Physics · 267 Zitationen · DOI
The cooling of p-nitroaniline (PNA), dimethylamino-p-nitroaniline (DPNA) and trans-stilbene (t-stilbene) in solution is studied experimentally and theoretically. Using the pump–supercontinuum probe (PSCP) technique we observed the complete spectral evolution of hot absorption induced by femtosecond optical pumping. In t-stilbene the hot S1 state results from Sn→S1 internal conversion with 50 fs characteristic time. The time constant of intramolecular thermalization or intramolecular vibrational redistribution (IVR) in S1 is estimated as τIVR≪100 fs. In PNA and DPNA the hot ground state is prepared by S1→S0 relaxation with characteristic time 0.3–1.0 ps. The initial molecular temperature is 1300 K for PNA and 860 K for t-stilbene. The subsequent cooling dynamics (vibrational cooling) is deduced from the transient spectra by assuming: (i) a Gaussian shape for the hot absorption band, (ii) a linear dependence of its peak frequency νm and width square Γ2 on molecular temperature T. Within this framework we derive analytic expressions for the differential absorption signal ΔOD(T(t),ν). After calibration with stationary absorption spectra in a low temperature range, the solute temperature T(t) may be evaluated from a transient absorption experiment. For highly polar PNA and DPNA, T(t) is well described by a biexponential decay which reflects local heating effects, while for nonpolar t-stilbene the local heating is negligible and the cooling proceeds monoexponentially. To rationalize this behavior, an analytic model is developed, which considers energy flow from the hot solute to a first solvent shell and then to the bulk solvent. Fastest cooling is found for PNA in water: a time constant of 0.64 ps (68%) corresponds to solute–solvent energy transfer while 2.0 ps (32%) characterizes the cooling of the first shell. In aprotic solvents cooling is slower than in alcohols and slows down further with decreasing solvent polarity. This contrasts with nonpolar t-stilbene which cools down with 8.5 ps both in acetonitrile and cyclohexane. Comparison of the cooling kinetics for PNA in water with those for DPNA in water-acetonitrile mixtures suggests that the solute–solvent energy transfer proceeds mainly through hydrogen bonds.
Chemical Physics Letters · 193 Zitationen · DOI
The Journal of Physical Chemistry B · 185 Zitationen · DOI
The photoisomerization of azobenzene in solution was studied experimentally and by calculations. trans-to-cis and cis-to-trans dynamics are described through broadband transient absorption, fluorescence, and stimulated Raman spectroscopy. Transient absorption was extended to cover not only the nπ* band but also the ππ* band in the ultraviolet. Isomerization yields are used for a quantitative comparison of trans and cis transient spectra under different excitation. For the trans-to-cis path upon nπ*(S(1)) excitation, the evolution develops with 0.3, 3, and 16 ps. The first two times reflect population relaxation to a local minimum S(1t )(L) and subsequent transition to a dark intermediate S(1t)(D) over an 8 kJ/mol barrier. The existence of stationary points S(1t)(L) and S(1t)(D) is confirmed by quantum-chemical calculations. The third time corresponds to S(1t) (D) → S0 relaxation to the ground state via an S1/S0 conical intersection over a 12 kJ/mol barrier. Thus, the 16 ps time constant is attributed to the isomerization process and not to vibrational cooling, contrary to the current view and in line with the previous interpretation by Lednev et al. (J. Phys. Chem. 1996, 100, 13338). The decay of the long-lived intermediate S(1t)(D) is consistent with the hula twist rather than with the inversion mechanism. For the cis-totrans reaction following nπ* excitation, signal decay is strongly nonexponential, with 0.1 and 1 ps. The latter (1 ps) is much shorter than the 16 ps decay of the trans isomer, implying different S1/S0 conical intersections and relaxation paths for the cis-totrans and trans-to-cis reaction. New results are also obtained with ππ*(Sn) excitation. Thus, for trans-azobenzene, 50% of the population relaxes to an S1 region, which is not accessible under nπ* excitation. For cis-azobenzene, up to 30% of the excited species isomerize to trans via an Sn/S1 intersection, resulting in a mixed cis/trans S1 population. The isomerization kinetics of azobenzene shows no viscosity dependence, putting into question the torsion mechanism and suggesting the hula-twist isomerization mechanism.
Journal of the American Chemical Society · 182 Zitationen · DOI
Photoinduced proton transfer (PT) from cations 6-hydroxyquinolinium (6HQc) and 6-hydroxy-1-methylquinolinium (6MQc) to water and alcohols, and solvation of the zwitterionic conjugate base 1-methylquinolinium-6-olate (6MQz) were studied with stationary and transient absorption spectroscopy and by quantum chemical calculations. Transient emission spectra from 6MQz in acetonitrile and protic solvents shift dynamically to the red without changing their shape and intensity. The shift matches the solvation correlation function C(t) either measured with known solvatochromic probes coumarin 343 and coumarin 153 or derived from infrared/dielectric-loss data on neat solvents. This indicates that 6MQz monitors the solvation dynamics and that no intramolecular electron transfer occurs on a subpicosecond or longer time scale. The PT dynamics S(t) from 6HQc and 6MQc closely follows C(t), being initially 2-3 times slower. This allows for the conclusion that PT is controlled by solvation, with a barrier of 2 kJ/mol. In water, a pre-condition of this ultrafast reaction seems to be hydrogen-bonding between the negatively charged oxygen and two water molecules, resulting in a complex 6HQc:H2O:H2O. The complex is stable due to a high (47 kJ/mol) bonding energy between 6HQc and a water molecule. In acetonitrile, the reaction equilibrium is strongly shifted to the cation. There an intermediate PT state was detected, which may be ascribed to the cationic form 6HQc:H2O due to residual water impurities. In water-acetonitrile mixtures, the ultrafast solvent-controlled PT is followed by a diffusion-controlled reaction; the measured rate kD approximately 1010 s-1 M-1 is characteristic for simple bimolecular diffusion. The dependence of the short-time PT signal on water concentration can be fitted with a Poisson distribution of water molecules around the cation. Altogether, the short-time and long-time behaviors provide strong evidence that diffusion of only one water molecule is sufficient to detach the proton. Subsequent solvent stabilization of the products completes the PT reaction.
The Journal of Physical Chemistry A · 163 Zitationen · DOI
The kinetics of the intramolecular charge-transfer (ICT) reaction of 4-(dimethylamino)benzonitrile (DMABN) in the polar solvent acetonitrile (MeCN) is investigated by fluorescence quantum yield and picosecond time-correlated single photon counting (SPC) experiments over the temperature range from -45 to +75 degrees C, together with femtosecond Sn <-- S1 transient absorption measurements at room temperature. For DMABN in MeCN, the fluorescence from the locally excited (LE) state is strongly quenched, with an unquenched to quenched fluorescence quantum yield ratio of 290 at 25 degrees C. Under these conditions, even very small amounts of the photoproduct 4-(methylamino)benzonitrile (MABN) severely interfere, as the LE fluorescence of MABN is in the same spectral range as that of DMABN. The influence of photoproduct formation could be overcome by a simultaneous analysis of the picosecond and photostationary measurements, resulting in data for the activation barriers Ea (5 kJ/mol) and Ed (32 kJ/mol) of the forward and backward ICT reaction as well as the ICT reaction enthalpy and entropy: DeltaH (-27 kJ/mol) and DeltaS [-38 J/(mol K)]. The reaction hence takes place over a barrier, with double-exponential fluorescence decays, as to be expected in a two-state reaction. From femtosecond transient absorption down to 200 fs, the LE and ICT excited state absorption (ESA) spectra of DMABN in n-hexane (LE) and in MeCN (LE and ICT) and also of 4-aminobenzonitrile in MeCN (LE) are obtained. For DMABN in MeCN, the quenching of the LE and the rise of the ICT ESA bands occurs with a single characteristic time of 4.1 ps, the same as the ICT reaction time found from the picosecond SPC experiments at 25 degrees C. The sharp ICT peak at 320 nm does not change its spectral position after a pump-probe delay time of 200 fs, which suggests that large amplitude motions do not take place after this time. The increase with time in signal intensity observed for the LE spectrum of DMABN in n-hexane between 730 and 770 nm, is attributed to solvent cooling of the excess excitation energy and not to an inverse ICT --> LE reaction, as reported in the literature.
The Journal of Physical Chemistry A · 159 Zitationen · DOI
Femtosecond transient absorption spectra of molecules in solution change when an ultrafast reaction creates a new product state, and coherent optical processes complicate the spectra during the pump pulse. A low-frequency vibration may also be found to modulate an absorption or emission band for the first few picoseconds. For singular value decomposition of the data one identifies the educt, intermediate, and product states by their temporal behavior and thereby determines the spectra associated with these photochemical species. Here we extend this method by introducing two additional “species”: the apparatus function and the low-frequency oscillation. Associated with the apparatus function is the coherent spectrum. The spectrum of oscillations is obtained directly by optimizing a generalized rotation matrix, without need of model functions. It consists of band derivatives times oscillation amplitudes and after integration assists in decomposing the transient absorption spectra. The method is demonstrated with the excited-state intramolecular proton transfer (ESIPT) reaction of 2,5-bis(2‘-benzoxazolyl)hydroquinone in tetrahydrofuran. Ultrafast optical pumping prepares the excited enol form of the molecule. Its blue stimulated emission band prior to the reaction is reported for the first time. The enol form reacts with 110 ± 15 fs time constant to the excited keto form which emits in the red. The latter is created with coherent excitation of an H-chelate-ring bending vibration of 118 cm-1 and the proton transfer occurs during the first half-cycle. The wave packet modulates the frequency for an excited-state absorption (ESA) band of the keto form and for its stimulated emission band, with initial frequency excursions of +130 cm-1 and −180 cm-1, respectively. The dominant ESA band is extracted quantitatively from the data. Intramolecular vibrational redistribution in the excited keto state is characterized by vibrational dephasing (0.89 ± 0.1 ps time constant) and a red shift of the ESA band (1.26 ± 0.1 ps). The spectra of all species are obtained and decomposed.
Review of Scientific Instruments · 154 Zitationen · DOI
A setup for pump/supercontinuum-probe spectroscopy is described which (i) is optimized to cancel fluctuations of the probe light by single-shot referencing, and (ii) extends the probe range into the near-uv (1000-270 nm). Reflective optics allow 50 μm spot size in the sample and upon entry into two separate spectrographs. The correlation γ(same) between sample and reference readings of probe light level at every pixel exceeds 0.99, compared to γ(consec)<0.92 reported for consecutive referencing. Statistical analysis provides the confidence interval of the induced optical density, ΔOD. For demonstration we first examine a dye (Hoechst 33258) bound in the minor groove of double-stranded DNA. A weak 1.1 ps spectral oscillation in the fluorescence region, assigned to DNA breathing, is shown to be significant. A second example concerns the weak vibrational structure around t=0 which reflects stimulated Raman processes. With 1% fluctuations of probe power, baseline noise for a transient absorption spectrum becomes 25 μOD rms in 1 s at 1 kHz, allowing to record resonance Raman spectra of flavine adenine dinucleotide in the S(0) and S(1) state.
Journal of the American Chemical Society · 148 Zitationen · DOI
Time-resolved Stokes shifts in a dye-containing oligonucleotide have been observed over the entire time range from 40 fs to 40 ns. The dynamics fit to a power law with a small exponent of 0.15. Similar relaxation has been seen in proteins but has not been anticipated in DNA. Distinct relaxation components due to specific subcomponents of the system, bulk water, bound water, counterions, backbone, bases, and so on, are not found. The various subcomponents may be so strongly coupled that their motions cannot be treated separately.
Journal of the American Chemical Society · 145 Zitationen · DOI
The dynamics of the electric fields in the interior of DNA are measured by using oligonucleotides in which a native base pair is replaced by a dye molecule (coumarin 102) whose emission spectrum is sensitive to the local electric field. Time-resolved measurements of the emission spectrum have been extended to a six decade time range (40 fs to 40 ns) by combining results from time-correlated photon counting, fluorescence up-conversion, and transient absorption. Recent results showed that when the reporter is placed in the center of the oligonucleotide, the dynamics are very broadly distributed over this entire time range and do not show specific time constants associated with individual processes (Andreatta, D.; et al. J. Am. Chem. Soc. 2005, 127, 7270). This paper examines an oligonucleotide with the reporter near its end. The broadly distributed relaxation seen before remains with little attenuation. In addition, a new relaxation with a well-defined relaxation time of 5 ps appears. This process is assigned to the rapid component of "fraying" at the end of the helix.
Angewandte Chemie International Edition · 125 Zitationen · DOI
A molecular dipole field (see picture) is created by femtosecond excitation of the title compound, and the response of the environment is observed by stimulated emission spectroscopy of the dye. Strong frequency modulation in the dynamic Stokes shift reflects coherent solvent motion. The IR spectrum of the solvent is related quantitatively to the experiment by dielectric continuum theory. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2005/z501397_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
Journal of the American Chemical Society · 124 Zitationen · DOI
Guanosine monophosphate (GMP) in aqueous solutions has been studied with femtosecond broad-band transient absorption spectroscopy and by quantum-mechanical calculations. The sample was excited at 267 or 287 nm and probed between 270 and 1000 nm with 100 fs resolution, for various pH values between 2 and 7. At pH 2, when the guanine ring is ground-state protonated (GMPH(+)), we observe isosbestic behavior indicating state-to-state relaxation. The relaxation is biexponential, tau(1) = 0.4 ps, tau(2) = 2.2 ps, and followed by slower internal conversion with tau(3) = 167 ps. For nonprotonated GMP in the pH range 7-4, we find biexponential decay in the region 400-900 nm (tau(1) = 0.22 ps, tau(2) = 0.9 ps), whereas, between 270 and 400 nm, the behavior is triexponential with one growing, tau(1) = 0.25 ps, and two decaying, tau(2) = 1.0 ps, tau(3) = 2.5 ps, components. The excited-state evolution is interpreted with the help of quantum-chemical calculations, performed at the time-dependent PBE0 level accounting for bulk solvent effects and specific solvation. The computed dynamics involves L(a) and L(b) bright excited states, whereas the n(0)pi* and pisigma* dark excited states play a minor role. Independent of the pH, the photoinduced evolution involves ultrafast L(b)-->L(a) conversion (tau(ba) << 100 fs) and exhibits the presence of a wide planar plateau on L(a). For neutral GMP a barrierless path connects this region to a conical intersection (CI) with the ground state, giving an account of the ultrafast decay of this species. For protonated GMPH(+) the system evolves into a stable minimum L(a min) characterized by out-of-plane displacement of NH and CH groups, which explains the longer (167 ps) fluorescence lifetime.
Chemical Physics Letters · 115 Zitationen · DOI
The Journal of Physical Chemistry A · 108 Zitationen · DOI
Betaine-30 in polar solvents was studied with the pump−supercontinuum probe technique after ca. 50 fs excitation at 532 and 634 nm. By monitoring the spectral evolution of stimulated emission, excited-state absorption, and bleaching, photoinduced solvation and ultrafast intramolecular rearrangement in the excited state are resolved for the first time. This rearrangement is related to intramolecular electron transfer (iET). In acetonitrile, the rate coefficient k of iET satisfies the condition of solvent control, k = 1/τ0 (±10%), where τ0 is a characteristic solvent relaxation time deduced from the solvation correlation function C(t). Back ET or internal conversion proceeds from a molecular conformation which differs from that in the ground state. It develops on a picosecond time scale and is followed by cooling of hot betaine molecules by the solvent. By comparing transient Stokes shift data with C(t), we extract solvation and intramolecular reorganization energies associated with high and low frequency optically active modes. The solvatochromism of betaine-30 contains substantial solvent-dependent intramolecular contributions and, therefore, cannot be understood without accounting for internal degrees of freedom.
Chemical Physics Letters · 106 Zitationen · DOI
Gold– and Platinum–Bismuth Donor–Acceptor Interactions Supported by an Ambiphilic PBiP Pincer Ligand
2012Angewandte Chemie International Edition · 105 Zitationen · DOI
Noble metals meet a heavyweight: A pincer ligand brings together bismuth with gold and platinum, so that metallophilic interactions are established. According to DFT calculations, these interactions contain dominant metal→bismuth contributions.
Chemical Physics Letters · 101 Zitationen · DOI
Angewandte Chemie International Edition · 100 Zitationen · DOI
The deposition of an atomically precise nanocluster, for example, Ag<sub>44</sub> (SR)<sub>30</sub> , onto a large-band-gap semiconductor such as TiO<sub>2</sub> allows a clear interface to be obtained to study charge transfer at the interface. Changing the light source from visible light to simulated sunlight led to a three orders of magnitude enhancement in the photocatalytic H<sub>2</sub> generation, with the H<sub>2</sub> production rate reaching 7.4 mmol h<sup>-1</sup> g<sub>catalyst</sub> <sup>-1</sup> . This is five times higher than that of TiO<sub>2</sub> modified with Ag nanoparticles and even comparable to that of TiO<sub>2</sub> modified with Pt nanoparticles under similar conditions. Energy band alignment and transient absorption spectroscopy reveal that the role of the metal clusters is different from that of both organometallic complexes and plasmonic nanoparticles: A type II heterojunction charge-transfer route is achieved under UV/Vis irradiation, with the cluster serving as a small-band-gap semiconductor. This results in the clusters acting as co-catalysts rather than merely photosensitizers.
Cellular Redox Activity of Coenzyme Q 10 : Effect of CoQ 10 Supplementation on Human Skeletal Muscle
2002Free Radical Research · 94 Zitationen · DOI
In this paper, we report results obtained from a continuing clinical trial on the effect of coenzyme Q10 (CoQ10) administration on human vastus lateralis (quadriceps) skeletal muscle. Muscle samples, obtained from aged individuals receiving placebo or CoQ10 supplementation (300mg per day for four weeks prior to hip replacement surgery) were analysed for changes in gene and protein expression and in muscle fibre type composition. Microarray analysis (Affymetrix U95A human oligonucleotide array) using a change in gene expression of 1.8-fold or greater as a cutoff point, demonstrated that a total of 115 genes were differentially expressed in six subject comparisons. In the CoQ10-treated subjects, 47 genes were up-regulated and 68 down-regulated in comparison with placebo-treated subjects. Restriction fragment differential display analysis showed that over 600 fragments were differentially expressed using a 2.0-fold or greater change in expression as a cutoff point. Proteome analysis revealed that, of the high abundance muscle proteins detected (2,086 +/- 115), the expression of 174 proteins was induced by CoQ10 while 77 proteins were repressed by CoQ10 supplementation. Muscle fibre types were also affected by CoQ10 treatment; CoQ10-treated individuals showed a lower proportion of type I (slow twitch) fibres and a higher proportion of type IIb (fast twitch) fibres, compared to age-matched placebo-treated subjects. The data suggests that CoQ10 treatment can act to influence the fibre type composition towards the fibre type profile generally found in younger individuals. Our results led us to the conclusion that coenzyme Q10 is a gene regulator and consequently has wide-ranging effects on over-all tissue metabolism. We develop a comprehensive hypothesis that CoQ10 plays a major role in the determination of membrane potential of many, if not all, sub-cellular membrane systems and that H2O2 arising from the activities of CoQ10 acts as a second messenger for the modulation of gene expression and cellular metabolism.
Angewandte Chemie International Edition · 92 Zitationen · DOI
Two-NIR-photon-triggered Z→E isomerization of an azobenzene was accomplished by covalently linking a two-photon-harvesting triarylamine antenna to a thermally stable ortho-fluorinated azobenzene derivative. The obtained photoswitch is fully addressable with visible and NIR light by using one-photon and two-photon excitation, respectively, with the latter offering enhanced penetration depth and improved spatial resolution.
The Journal of Physical Chemistry A · 90 Zitationen · DOI
p-Nitroaniline (pNA) was examined with the semiempirical SAM1 Hamiltonian in vacuo and in water. Geometry optimizations were performed in the ground and the lowest excited state along the −NH2 wagging and the −NO2 twisting coordinate. The latter is shown to play a key role in the spectroscopy and dynamics of pNA. The strong charge-transfer (CT) absorption band is conformationally broadened. Red-edge excitation prepares the CT state with a distribution of −NO2 conformations which is concentrated around the coplanar conformation with the benzene moiety. In water, C-amino and C-nitro stretching vibrations are also excited. The structural reorganization along those modes is assumed to occur on the same time scale as ultrafast polar solvation. In this case the relaxation dynamics in water after ∼100 fs consists mainly in an evolution of the −NO2 twist distribution toward a deep minimum at the perpendicular conformation; the dipole moment change during that process has an upper limit of 2 D. Stimulated emission is observable for the first few hundred femtoseconds. Thereafter a multidimensional conical intersection with the ground state is reached. The S1 population decay can be monitored independent from the twisting process by observing excited-state absorption at 4 eV. All of these predictions are consistent with recent pump/supercontinuum probe measurements of pNA in water.
Mutation research. Fundamental and molecular mechanisms of mutagenesis · 78 Zitationen · DOI
The Journal of Chemical Physics · 78 Zitationen · DOI
Transient absorption and gain spectra of the styryl dye LDS-750 in solution have been studied by the pump/supercontinuum probe (PSCP) technique with excitation at 530 nm. The pump/probe intensity correlation width was 70 fs, providing a time resolution of 40 fs. Spectra were detected in the range 400–800 nm with 1.5 nm resolution. Before 70 fs, prominent spectral structure is observed due to resonant Raman scattering from a 1500 cm−1 active mode of the chromophore. At later time, the gain spectrum undergoes an ultrafast redshift and change of shape, with time constants of ∼200 and ∼600 fs for acetonitrile and chloroform solutions, respectively. At high pumping energy (1.2 μJ), the final emitting state is reached by internal conversion from higher electronic states without a further essential Stokes shift. The emitting state is assigned to an excited isomeric form of the molecule. At low pumping energy (0.3 μJ), the first excited electronic state isomerizes in an ultrafast process followed by a slower process, the dynamics of which is controlled by the solvent. The geometrical and electronic nature of these processes and their coupling to the solvent needs further clarification.
The Journal of Physical Chemistry B · 75 Zitationen · DOI
Photoinduced isomerization of 1,1'-bis-indanyliden (stiff-stilbene) in solution was studied with broadband transient absorption and femtosecond Raman spectroscopies, and by quantum-chemical calculations. Trans-to-cis S1 isomerization proceeds over a 600 and 400 cm(-1) barrier in n-hexane and acetonitrile, respectively. The reaction develops on multiple time scales with fast (0.3-0.4 ps) viscosity-independent and slower (2-26 ps) viscosity-dependent components. In the course of intramolecular torsion (which should be the main reaction coordinate) some excited molecules pass through the perpendicular conformation P and reach the cis geometry, to be temporarily trapped there. Subsequently they relax back to P and further to the ground state S0. The cis-to-trans isomerization reveals ultrafast (0.06 ps) oscillatory relaxation followed by 13 ps decay in n-hexane and 2 ps decay in acetonitrile, corresponding to barriers of 800 and 400 cm(-1), respectively. Raman S0 and S1 spectra are reported and discussed. The perpendicular conformation P was not detected, possibly due to its low oscillator strength and short lifetime, or because of strong overlap with hot product spectra. XMCQDPT2 calculations locate a stationary S1 point on the cis side and two perpendicular-pyramidalized stationary points, to be reached from the former over 300 and 680 cm(-1) barrier. Implications for parent stilbene are discussed; in this case we also see evidence for the trans-to-cis adiabatic path, as in stiff-stilbene. Very similar viscosity dependence for the two compounds supports the common isomerization pathway: torsion about the central double bond.
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- Dr. Sergey Kovalenko
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- Mathematisch-Naturwissenschaftliche Fakultät
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- Institut für Chemie
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- Physikalische Chemie - Spektroskopie
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