Sergey A. Kovalenko

Cooling dynamics of an optically excited molecular probe in solution from femtosecond broadband transient absorption spectroscopy

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 de...

Femtosecond relaxation of photoexcited para-nitroaniline: solvation, charge transfer, internal conversion and cooling

Abstract The ultrafast relaxation of p -nitroaniline (PNA) in water and acetonitrile is studied experimentally and theoretically. Transient absorption spectra are measured by the pump–supercontinuum probe technique (PSCP) after 50 fs excitation at 400 nm. The relaxation includes several stages with distinct time scales: solvation, intramolecular charge transfer (CT), internal conversion and cooling. The spectral evolution before 100 fs reflects mainly solvation with dynamic Stokes shift of 3500 cm −1 in acetonitrile and 4000 cm −1 in water. CT and internal conversion are governed by twisting of the –NO 2 group and proceed in water with 120 and 250 fs, respectively. A hot ground state upon internal conversion is characterized by an initial temperature of 1400 K. The subsequent solute–solvent energy transfer is characterized by exponential behavior between 1 and 3 ps and by a nonexponential decay at longer delays, the solute cooling time lies in the range 0.85–1.3 ps.

ortho-Fluoroazobenzenes: Visible Light Switches with Very Long-Lived Z Isomers

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 NN 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.

Ultrafast strokes shift and excited-state transient absorption of coumarin 153 in solution

Abstract Transient absorption and gain spectra of coumarin 153 in polar solvents are studied by the pump/supercontinuum probe (PSCP) technique with 40 fs time resolution. Vibrational frequencies in the ground and excited state of the chromophore are obtained from the early transient spectra. At later time, the gain band experiences a considerable red shift with two isosbestic points which appear successively, while a pronounced excited-state absorption band at 428 nm changes only negligibly. These observations are compared to the results from semi-empirical calculations for higher excited states. They are not fully consistent with relaxation due to pure solvation and may indicate an intramolecular process.

Photoinduced dynamics of guanosine monophosphate in water from broad-band transient absorption spectroscopy and quantum-chemical calculations.

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.

FEMTOSECOND HOLE-BURNING SPECTROSCOPY OF THE DYE DCM IN SOLUTION : THE TRANSITION FROM THE LOCALLY EXCITED TO A CHARGE-TRANSFER STATE

Abstract Transient spectra of the styryl dyM (4-dicyanomethylene-2-methyl-6- p -dimethylaminostyryl-4H-pyran) in methanol were studied by the pump-supercontinuum probe technique with 40 fs time resolution. A theory of measurements with a supercontinuum probe is presented. Gain and absorption spectra were measured from 400 to 800 nm with 1.5 nm resolution. Before 70 fs, prominent spectral structure is observed which is mainly due to resonant Raman processes. At longer times the spectrum undergoes a red shift and change of shape (time constant 140 fs) with a well-defined isosbestic point. After 300 fs solvation becomes apparent. The early transient spectrum is assigned to the locally excited state of DCM.

Dynamic Polar Solvation Is Reported by Fluorescing 4-Aminophthalimide Faithfully Despite H-Bonding

Solvation dynamics of 4-aminophthalimide (4AP) in methanol is measured by broadband upconversion of the fluorescence band. The peak emission frequency nu(t) is determined from 100 fs onward with 85 fs time resolution. Polar solvation based on simple continuum theory, including solute polarizability, describes the temporal shape of nu(t) quantitatively. Extrapolation nu(t-->0) points to an initial emission frequency which agrees with the result from stationary spectroscopy in a nonpolar solvent. The extent (4300 cm(-1)) of the dynamic Stokes shift is largely due (50%) to H-bonding, however. The observations imply that H-bonds with 4AP adiabatically follow the dielectric relaxation of the methanol network. The stimulated emission band is also used to measure solvation dynamics. The evolving band is monitored by transient absorption spectroscopy of supercontinuum probe pulses. But the excited-state absorption spectrum, its relative amplitude, and its evolution are needed to extract nu(t) from such measurements. These key data are obtained by comparison with the upconversion results. Thus calibrated photometrically, 4AP transient absorption can be used to monitor solvation dynamics in any solvent. The excited-state absorption spectrum is assigned with the help of time-dependent density-functional calculations. Fluorescence excitation and double-resonance spectroscopy of isolated 4AP, cooled in a supersonic jet, is used to determine optically active modes. An intramolecular reorganization energy is inferred which is consistent with the value in 2-methylbutane (2025 cm(-1)). The crystal structure is also provided.

Gold– and Platinum–Bismuth Donor–Acceptor Interactions Supported by an Ambiphilic PBiP Pincer Ligand

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.

Photoisomerization dynamics and pathways of trans- and cis-azobenzene in solution from broadband femtosecond spectroscopies and calculations.

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.

Broad-band fluorescence upconversion for femtosecond spectroscopy

With near-infrared gating and improved light collection geometry, the entire fluorescence band can be upconverted in a broad range of 10 000 cm−1 without readjusting optical elements, thus allowing measurements with a single pump-gate scan. Monitoring of the pump-induced white light continuum provides for the time correction of the up-converted fluorescence spectra. The overall time resolution is then limited by the pump-gate cross correlation. The technique is illustrated with the femtosecond evolution of fluorescence from two molecular probes in solution.