Directly meso-meso linked porphyrin rings: synthesis, characterization, and efficient excitation energy hopping

Directly meso-meso linked porphyrin rings CZ4, CZ6, and CZ8 that respectively comprise four, six, and eight porphyrins have been synthesized in a stepwise manner from a 5,10-diaryl zinc(II) porphyrin building block. Symmetric cyclic structures have been indicated by their very simple (1)H NMR spectra that exhibit only a single set of porphyrin and their absorption spectra that display a characteristic broad nonsplit Soret band around 460 nm. Energy minimized structures calculated at the B3LYP/6-31G* level indicate that a dihedral angle between neighboring porphyrins decreases in order of CZ6 > CZ8 > CZ4, which is consistent with the (1)H NMR data. Photophysical properties of these molecules have been examined by the steady-state absorption, fluorescence, fluorescence lifetime, fluorescence anisotropy decay, and transient absorption measurements. Both the pump-power dependence on the femtosecond transient absorption and the transient absorption anisotropy decay profiles are directly related with the excitation energy migration processes within the porphyrin rings, where the exciton-exciton annihilation time and the polarization anisotropy rise time are well described in terms of the Forster-type incoherent energy hopping model. Consequently, the excitation energy hopping rates have been estimated for CZ4 (119 +/- 2 fs)(-)(1), CZ6 (342 +/- 59 fs)(-)(1), and CZ8 (236 +/- 31 fs)(-)(1), which reflect the magnitude of the electronic coupling between the neighboring porphyrins. Overall, these porphyrin rings serve as a well-defined wheel-shaped light harvesting antenna model in light of very efficient excitation energy hopping along the ring.     

Ultrafast fluorescence depolarisation in the yellow fluorescent protein due to its dimerisation.

Transient absorption spectroscopy with sub-100 fs time resolution was performed to investigate the oligomerisation behaviour of eYFP in solution. A single time constant tau(AD)=2.2+/-0.15 ps is sufficient to describe the time-resolved anisotropy decay up to at least 200 ps. The close contact of two protein barrels is deduced as the exclusive aggregation state in solution. From the final anisotropy r(infinity)=0.28+/-0.02, the underlying quaternary structure can be traced back to the somewhat distorted structure of the dimers of wt-GFP. The use of autofluorescent proteins as rulers in F?rster resonance energy transfer (FRET) measurements may demand polarisation-sensitive detection of the fluorescence with high time resolution.     

Femtosecond dynamics of excited-state intramolecular proton transfer in <Emphasis Type="Italic">o</Emphasis>-tosylaminobenzaldehyde

Dynamics of excited-state intramolecular proton transfer (ESIPT) in o-tosylaminobenzaldehyde has been studied by femtosecond absorption spectroscopy with a time resolution of 30 fs. The characteristic time of this process is ∼100 fs. Differential absorption rate curves exhibit oscillations that are consistent with theoretically predicted ESIPT-promoting vibrational modes. Efficient nonradiative deactivation with a rate constant of 6.25 × 10¹⁰ s⁻¹ occurs in the excited product of proton transfer, with internal rotation followed by intersystem crossing being one of the feasible deactivation pathways.     

Subpicosecond protein backbone changes detected during the green-absorbing proteorhodopsin primary photoreaction

Recent studies demonstrate that photoactive proteins can react within several picoseconds to photon absorption by their chromophores. Faster subpicosecond protein responses have been suggested to occur in rhodopsin-like proteins where retinal photoisomerization may impulsively drive structural changes in nearby protein groups. Here, we test this possibility by investigating the earliest protein structural changes occurring in proteorhodopsin (PR) using ultrafast transient infrared (TIR) spectroscopy with approximately 200 fs time resolution combined with nonperturbing isotope labeling. PR is a recently discovered microbial rhodopsin similar to bacteriorhodopsin (BR) found in marine proteobacteria and functions as a proton pump. Vibrational bands in the retinal fingerprint (1175-1215 cm(-1)) and ethylenic stretching (1500-1570 cm(-1)) regions characteristic of all-trans to 13-cis chromophore isomerization and formation of a red-shifted photointermediate appear with a 500-700 fs time constant after photoexcitation. Bands characteristic of partial return to the ground state evolve with a 2.0-3.5 ps time constant. In addition, a negative band appears at 1548 cm(-1) with a time constant of 500-700 fs, which on the basis of total-15N and retinal C15D (retinal with a deuterium on carbon 15) isotope labeling is assigned to an amide II peptide backbone mode that shifts to near 1538 cm(-1) concomitantly with chromophore isomerization. Our results demonstrate that one or more peptide backbone groups in PR respond with a time constant of 500-700 fs, almost coincident with the light-driven retinylidene chromophore isomerization. The protein changes we observe on a subpicosecond time scale may be involved in storage of the absorbed photon energy subsequently utilized for proton transport.     

Femtosecond dynamics of the ring closing process of diarylethene: a case study of electrocyclic reactions in photochromic single crystals

The cyclization reaction of the photochromic diarylethene derivative 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)perfluorocyclopentene was studied in its single crystal phase with femtosecond transient absorption spectroscopy. The transient absorption measurements were performed with a robust acquisition scheme that explicitly exploits the photoreversibility of the molecular system and monitors the reversibility conditions. The crystalline system demonstrated 3 × 10(4) repeatable cycles before significant degradation was observed. Immediately following photoexcitation, the excited state absorption associated with the open-ring conformation undergoes a large spectral shift with a time constant of approximately 200 fs. Following this evolution on the excited state potential energy surface, the ring closure occurs with a time constant of 5.3 ps, which is significantly slower than previously reported measurements for similar derivatives in the solution phase. Time resolved electron diffraction studies were used to further demonstrate the assignment of the transient absorption dynamics to the ring closing reaction. The mechanistic details of the ring closing are discussed in the context of prior computational work along with a vibrational mode analysis using density functional theory to give some insight into the primary motions involved in the ring closing reaction.     

Excited-state absorption and ultrafast relaxation dynamics of porphyrin, diprotonated porphyrin, and tetraoxaporphyrin dication

The relaxation dynamics of unsubstituted porphyrin (H2P), diprotonated porphyrin (H4P2+), and tetraoxaporphyrin dication (TOxP2+) has been investigated in the femtosecond-nanosecond time domain upon photoexcitation in the Soret band with pulses of femtosecond duration. By probing with spectrally broad femtosecond pulses, we have observed transient absorption spectra at delay times up to 1.5 ns. The kinetic profiles corresponding with the band maxima due to excited-state absorption have been determined for the three species. Four components of the relaxation process are distinguished for H2P: the unresolvably short B --> Qy internal conversion is followed by the Qy --> Qx process, vibrational relaxation, and thermalization in the Qx state with time constant approximately 150 fs, 1.8 ps, and 24.9 ps, respectively. Going from H2P to TOxP2+, two processes are resolved, i.e., B --> Q internal conversion and thermal equilibration in the Q state. The B --> Q time constant has been determined to be 25 ps. The large difference with respect to the B --> Qy time constant of H2P has been related to the increased energy gap between the coupled states, 9370 cm-1 in TOxP2+ vs 6100 cm-1 in H2P. The relaxation dynamics of H4P2+ has a first ultrafast component of approximately 300 fs assigned as internal conversion between the B (or Soret) state and charge-transfer (CT) states of the H4P2+ complex with two trifluoroacetate counterions. This process is followed by internal CT --> Q conversion (time constant 9 ps) and thermalization in the Q state (time constant 22 ps).     

Molecular reorientation of liquid water studied with femtosecond midinfrared spectroscopy

The molecular reorientation of liquid water is key to the hydration and stabilization of molecules and ions in aqueous solution. A powerful technique to study this reorientation is to measure the time-dependent anisotropy of the excitation of the O-H/O-D stretch vibration of HDO dissolved in D2O/H2O using femtosecond midinfrared laser pulses. In this paper, we present and discuss experiments in which this technique is used to study the correlation between the molecular reorientation of the water molecules and the strength of the hydrogen-bond interactions. On short time scales (<200 fs), it was found that the anisotropy shows a partial decay due to librational motions of the water molecules that keep the hydrogen bond intact. On longer time scale (>200 fs), the anisotropy shows a complete decay with an average time constant of 2.5 ps. From the frequency dependence of the anisotropy dynamics, it follows that a subensemble of the water molecules shows a fast reorientation that is accompanied by a large change of the vibrational frequency. This finding agrees with the molecular jumping mechanism for the reorientation of liquid water that has recently been proposed by Laage and Hynes.     

Study of acyl group migration by femtosecond transient absorption spectroscopy and computational chemistry

The primary photophysical and photochemical processes in the photochemistry of 1-acetoxy-2-methoxyanthraquinone (1a) were studied using femtosecond transient absorption spectroscopy. Excitation of 1a at 270 nm results in the population of a set of highly excited singlet states. Internal conversion to the lowest singlet npi* excited state, followed by an intramolecular vibrational energy redistribution (IVR) process, proceeds with a time constant of 150 +/- 90 fs. The 1npi* excited state undergoes very fast intersystem crossing (ISC, 11 +/- 1 ps) to form the lowest triplet pipi* excited state which contains excess vibrational energy. The vibrational cooling occurs somewhat faster (4 +/- 1 ps) than ISC. The primary photochemical process, migration of acetoxy group, proceeds on the triplet potential energy surface with a time constant of 220 +/- 30 ps. The transient absorption spectra of the lowest singlet and triplet excited states of 1a, as well as the triplet excited state of the product, 9-acetoxy-2-methoxy-1,10-anthraquinone (2a), were detected. The assignments of the transient absorption spectra were supported by time-dependent DFT calculations of the UV-vis spectra of the proposed intermediates. All of the stationary points for acyl group migration on the triplet and ground state singlet potential energy surfaces were localized, and the influence of the acyl group substitution on the rate constants of the photochemical and thermal processes was analyzed.     

Femtosecond spectroscopic studies of the one- and two-photon excited-state dynamics of 2,2,17,17-tetramethyloctadeca-5,9,13-trien-3,7,11,15-tetrayne: a trimeric oligodiacetylene

The excited-state dynamics of an oligomer of polydiacetylene, 2,2,17,17-tetramethyloctadeca-5,9,13-trien-3,7,11,15-tetrayne, dissolved in n-hexane have been studied by femtosecond fluorescence upconversion and polarized transient absorption experiments under one- and two-photon excitation conditions. Spectroscopically monitoring the population relaxation in the excited states in real time results in a distinct time separation of the dynamics. It has been concluded that the observed dynamics can be fully accounted for on the basis of the two lower excited states of the target molecule. The S1 (2(1)Ag) state, which cannot be excited from the ground state with one-photon absorption, is verified to be populated via internal conversion in 200+/-40 fs from the strong dipole-allowed S2 (1(1)Bu) state. The population in the "hot" S1 state subsequently cools with a time constant of 6+/-1 ps and decays back to the ground state with a lifetime of 790+/-12 ps.     

Vibrational and orientational dynamics of water in aqueous hydroxide solutions

We report the vibrational and orientational dynamics of water molecules in isotopically diluted NaOH and NaOD solutions using polarization-resolved femtosecond vibrational spectroscopy and terahertz time-domain dielectric relaxation measurements. We observe a speed-up of the vibrational relaxation of the O-D stretching vibration of HDO molecules outside the first hydration shell of OH(-) from 1.7 ± 0.2 ps for neat water to 1.0 ± 0.2 ps for a solution of 5 M NaOH in HDO:H(2)O. For the O-H vibration of HDO molecules outside the first hydration shell of OD(-), we observe a similar speed-up from 750 ± 50 fs to 600 ± 50 fs for a solution of 6 M NaOD in HDO:D(2)O. The acceleration of the decay is assigned to fluctuations in the energy levels of the HDO molecules due to charge transfer events and charge fluctuations. The reorientation dynamics of water molecules outside the first hydration shell are observed to show the same time constant of 2.5 ± 0.2 ps as in bulk liquid water, indicating that there is no long range effect of the hydroxide ion on the hydrogen-bond structure of liquid water. The terahertz dielectric relaxation experiments show that the transfer of the hydroxide ion through liquid water involves the simultaneous motion of ~7 surrounding water molecules, considerably less than previously reported for the proton.     

Excited-state decay of hydrocarbon radicals, investigated by femtosecond time-resolved photoionization: ethyl, propargyl, and benzyl

The excited state decay of the hydrocarbon radicals ethyl, C(2)H(5); propargyl, C(3)H(3); and benzyl, C(7)H(7) was investigated by femtosecond time-resolved photoionization. Radicals were generated by flash pyrolysis of n-propyl nitrite, propargyl bromide, and toluene, respectively. It is shown that the 2 (2)A(') (3s) Rydberg state of ethyl excited at 250 nm decays with a time constant of 20 fs. No residual signal was observed at longer delay times. For the 3 (2)B(1) state of propargyl excited at 255 nm a slower decay with a time constant 50+/-10 fs was determined. The 4 (2)B(2) state of benzyl excited at 255 nm decays within 150+/-30 fs.     

DNA excited-state dynamics: ultrafast internal conversion and vibrational cooling in a series of nucleosides

To better understand DNA photodamage, several nucleosides were studied by femtosecond transient absorption spectroscopy. A 263-nm, 150-fs ultraviolet pump pulse excited each nucleoside in aqueous solution, and the subsequent dynamics were followed by transient absorption of a femtosecond continuum pulse at wavelengths between 270 and 700 nm. A transient absorption band with maximum amplitude near 600 nm was detected in protonated guanosine at pH 2. This band decayed in 191 +/- 4 ps in excellent agreement with the known fluorescence lifetime, indicating that it arises from absorption by the lowest excited singlet state. Excited state absorption for guanosine and the other nucleosides at pH 7 was observed in the same spectral region, but decayed on a subpicosecond time scale by internal conversion to the electronic ground state. The cross section for excited state absorption is very weak for all nucleosides studied, making some amount of two-photon ionization of the solvent unavoidable. The excited state lifetimes of Ado, Guo, Cyd, and Thd were determined to be 290, 460, 720, and 540 fs, respectively (uncertainties are +/-40 fs). The decay times are shorter for the purines than for the pyrimidine bases, consistent with their lower propensity for photochemical damage. Following internal conversion, vibrationally highly excited ground state molecules were detected in experiments on Ado and Cyd by hot ground state absorption at ultraviolet wavelengths. The decays are assigned to intermolecular vibrational energy transfer to the solvent. The longest time constant observed for Ado is approximately 2 ps, and we propose that solute-solvent H-bonds are responsible for this fast rate of vibrational cooling. The results show for the first time that excited singlet state dynamics of the DNA bases can be directly studied at room temperature. Like sunscreens that function by light absorption, the bases rapidly convert dangerous electronic energy into heat, and this property is likely to have played a critical role in life's early evolution on earth.     

Is Water Physisorption Reversible for TiO_2 Nanocrystals？ A Combinational Spectral Study

In this work,the nature of physisorbed water and its impacts on the structure,surface chemistry,and proton conduction properties of TiO2 nanocrystals were investigated by a combinational spectral technique.All TiO2 nanocrystals were directly prepared by a hydrothermal method,which showed highly hydrated and sulfated surfaces.The surface water molecules were indicated to exist in a wide set of energetically nonequivalent surface hydration groups,leading to the removal of physisorbed and chemisorbed water in sequence with increasing temperature.After heating treatment at 100 ℃ in air,physisorbed water layers were recovered with no significant impacts on the TiO2 nanostructure.On the other hand,when treated at the same temperature in vacuum,the recovery of physisorbed water layers was partially reversible,while a new hydration state appeared due to the filling of the high-energy adsorption sites by water molecules,which led to a significant increase in the amount of water molecules for surface hydration and an accelerated dehydration process toward lower temperature.As a result,an abnormal increase was observed in proton conductivity.These observations were explained in terms of thermally induced changes of surface chemistry and the amount of hydrated water.The results reported in this work are important,which may help understand the roles that the physisorbed water plays in stabilizing the nanostructures and therefore could have a broad class of implications.     

State-resolved dynamics of the CH(A2Delta) channels from single and multiple photon dissociation of bromoform in the 10-20 eV energy range

Single photon dissociation of bromoform using synchrotron radiation has been investigated by Fourier transform visible fluorescence spectroscopy (FTVIS). The photodissociation of bromoform in the 12-18 eV energy range results in several products, among which are the CH(A2Delta) and CH(B2Sigma) radicals. Vibrational and rotational state distributions of the CH(A2Delta) are determined from their fluorescence spectra. From the threshold photon energy above which emission from the CH(A2Delta) radicals is observed, the most likely process leading to CH(A) formation is CHBr3 --> CH + 3Br rather than CHBr3 --> CH + Br + Br2. The rotational Boltzmann temperatures in the CH(A --> X) emission spectra for v' = 0 and v' = 1 range between 1570 and 3650 K, depending on the excitation photon energy. From the high rotational excitation, the results suggest that the mechanism for the loss of three bromine atoms is most likely sequential. A small negative emission anisotropy of the CH(A) radicals [(Ipar - Iper)/(Ipar + 2Iper) = -0.024 +/- 0.005] is constant across the action spectrum; a small net absorption dipole of CHBr3 in the vacuum ultraviolet is parallel to the 3-fold symmetry axis of the CHBr3 molecule. The state distributions of the CH(A2Delta) radicals from multiphoton dissociation of bromoform using the 266 nm output (three photons) of a femtosecond laser (Boltzmann temperatures: T(v'=0)(rot)= 4250 +/- 300 K; T(v'=1)(rot)= 3100 +/- 550 K) are compared to those from the single photon dissociation results (Boltzmann temperatures: T(v'=0)(rot)= 3650 +/- 150 K; T(v'=1)(rot)= 2400 +/- 200 K) at the same total excitation energy under collision free conditions. The analysis of the CH(A) rotational populations shows hotter rotational populations for the femtosecond experiment, also suggesting sequential dissociation of the bromoform in the femtosecond experiment. The duration of the femtosecond laser pulse is approximately 180 fs, setting a limit on the time scales for the multiple dissociations.     

Probing electron transfer dynamics at MgO surfaces by Mg-atom desorption

Ultraviolet excitation of high surface area MgO films using 4.7 eV femtosecond pulses results in neutral Mg-atom desorption with hyperthermal kinetic energies in the range 0.1-0.4 eV. The Mg-atom hyperthermal energies and power dependences are similar to those previously observed using nanosecond pulsed excitation. Femtosecond two-pulse correlation measurements reveal the existence of different dynamical paths for Mg-atom desorption. One mechanism displays a sub-150 fs time scale and involves the simultaneous or near-simultaneous transition of two electrons to a 3-coordinated Mg(2+) site. Other paths display picosecond time scales that we associate with dynamics following electron trapping at 3-coordinated Mg(2+) surface sites.     

Ultrafast vibrational dynamics of adenine-thymine base pairs in DNA oligomers

N-H stretching excitations of DNA oligomers containing 23 alternating adenine-thymine base pairs are studied in femtosecond two-color pump-probe experiments. For a DNA film in a zero relative humidity atmosphere, transient vibrational spectra and their time evolution up to 10 ps demonstrate negligible spectral diffusion and allow for discerning different N-H stretching bands and the O-H stretching absorption of residual water molecules. Lifetimes on the order of 0.5 ps are found for both N-H and O-H stretching modes. The time-dependent pump-probe anisotropies of the different N-H excitations point to a pronounced coupling among them, whereas the O-H stretching anisotropy remains essentially constant.     

Ultrafast intramolecular charge transfer with strongly twisted aminobenzonitriles: 4-(di-tert-butylamino)benzonitrile and 3-(di-tert-butylamino)benzonitrile

The newly synthesized aminobenzonitriles with two bulky amino substituents 4-(di-tert-butylamino)benzonitrile (DTABN) and 3-(di-tert-butylamino)benzonitrile (mDTABN) have strongly twisted amino groups in the ground state. From X-ray crystal analysis it is found that the amino twist angle theta of mDTABN equals 86.5 degrees , whereas a twist angle of around 75 degrees is deduced for DTABN from the extinction coefficient of its lowest-energy absorption band in n-hexane. Because of the electronic decoupling between the amino and benzonitrile groups caused by these large twist angles, the absorption of DTABN and mDTABN is relatively weak below 40000 cm-1, with extinction coefficients around 25 times smaller than those of the planar 4-(dimethylamino)benzonitrile (DMABN). DTABN as well as mDTABN undergo efficient intramolecular charge transfer (ICT) in the singlet excited state, in nonpolar (n-hexane) as well as in polar (acetonitrile) solvents. Their fluorescence spectra consist of an ICT emission band, without evidence for locally excited (LE) fluorescence. The occurrence of efficient ICT with mDTABN is different from the findings with all other N,N-dialkylaminobenzonitriles in the literature, for which ICT only appears with the para-derivative. From solvatochromic measurements, an ICT dipole moment of 17 D is determined for DTABN as well as for mDTABN, similar to that of DMABN. The picosecond fluorescence decays of DTABN (time resolution 3 ps) are effectively single exponential. Their decay time is equal to the ICT lifetime tau'0(ICT), which increases with solvent polarity from 0.86 ns in n-hexane to 3.48 ns in MeCN at 25 degrees C. The femtosecond excited-state absorption (ESA) spectra of DTABN in n-hexane and MeCN at 22 degrees C show a decay of the LE and a corresponding rise of the ICT absorption. The ICT reaction time is 70 fs in n-hexane and 60 fs in MeCN. DTABN and mDTABN may have a strongly twisted ICT state, similar to that of 6-cyanobenzoquinuclidine but different from that of DMABN.     

Femtosecond time-resolved optical and Raman spectroscopy of photoinduced spin crossover: temporal resolution of low-to-high spin optical switching

A combination of femtosecond electronic absorption and stimulated Raman spectroscopies has been employed to determine the kinetics associated with low-spin to high-spin conversion following charge-transfer excitation of a FeII spin-crossover system in solution. A time constant of tau = 190 +/- 50 fs for the formation of the 5T2 ligand-field state was assigned based on the establishment of two isosbestic points in the ultraviolet in conjunction with changes in ligand stretching frequencies and Raman scattering amplitudes; additional dynamics observed in both the electronic and vibrational spectra further indicate that vibrational relaxation in the high-spin state occurs with a time constant of ca. 10 ps. The results set an important precedent for extremely rapid, formally forbidden (DeltaS = 2) nonradiative relaxation as well as defining the time scale for intramolecular optical switching between two electronic states possessing vastly different spectroscopic, geometric, and magnetic properties.     

飞秒时间分辨的光电子影像研究氯化苄分子内转换动力学(英文)

结合时间分辨的飞秒光电子影像(TRPEI)技术和时间分辨的质谱技术,研究了氯化苄(BzCl)分子内转换动力学过程.从光电子影像中获得了光电子动能分布和角度分布.氯化苄分子吸收两个400nm的光子后从基态跃迁到S4态和S2态.获得的母体离子随泵浦-探测时间延迟变化的曲线可以用两个指数函数进行拟合,包括一个时间常数为50fs的快速组分和一个时间常数为910fs的慢速组分.通过分析光电子动能分布随延迟时间的变化,我们认为分子被激发到S4态后在很短的时间内与S2态发生耦合迅速弛豫到S2态,然后再经内转换(IC)弛豫到S1态.最初布居的激发态分子经过内转换弛豫到S1态的时间尺度为50fs.910fs的慢速时间组分反映了分子弛豫到S1态后,经内转换向基态S0的弛豫.光电子角度分布的各向异性参数从零时刻的0.87增加到25fs时的0.94,然后逐渐减小到190fs时刻的0.59的现象,也反映了氯化苄分子从S4态耦合到S2态,然后内转换到S1态的动力学过程.     

Excited State Intramolecular Proton Transfer of 1-Hydroxyanthraquinone

The excited state intra-molecular proton transfer dynamics of 1-hydroxyanthraquinone in solution are investigated by femtosecond transient absorption spectroscopy and quantum chemistry calculations. Two characteristic bands of excited state absorption and stimu-lated emission are observed in transient absorption spectra with the excitation by the pump wavelength of 400 nm. From the delayed stimulated emission signal, the time scale of the intra-molecular proton transfer is determined to be about 32 fs. The quantum chemistry calculations show that the molecular orbits and the order of the S₂ and S₁ states are rever-sal and a conical intersection is demonstrated to exist along the proton transfer coordinate. After proton transfer, the second excited state of tautomer populated via the conical intersection undergoes the internal conversion with ～200 fs and the following intermolecular energy relaxation with ～16 ps. The longer component 300 ps can be explained in terms of the relaxation from excited-state tautomer to its ground state. From our observations, two proton transfer pathways via a conical intersection are proposed and the dominated one preserves the molecular orbits.