Majed Chergui

Femtosecond XANES Study of the Light-Induced Spin Crossover Dynamics in an Iron(II) Complex

X-ray absorption spectroscopy is a powerful probe of molecular structure, but it has previously been too slow to track the earliest dynamics after photoexcitation. We investigated the ultrafast formation of the lowest quintet state of aqueous iron(II) tris(bipyridine) upon excitation of the singlet metal-to-ligand-charge-transfer (1MLCT) state by femtosecond optical pump/x-ray probe techniques based on x-ray absorption near-edge structure (XANES). By recording the intensity of a characteristic XANES feature as a function of laser pump/x-ray probe time delay, we find that the quintet state is populated in about 150 femtoseconds. The quintet state is further evidenced by its full XANES spectrum recorded at a 300-femtosecond time delay. These results resolve a long-standing issue about the population mechanism of quintet states in iron(II)-based complexes, which we identify as a simple 1MLCT→3MLCT→5T cascade from the initially excited state. The time scale of the 3MLCT→5T relaxation corresponds to the period of the iron-nitrogen stretch vibration.

Electron and X‐Ray Methods of Ultrafast Structural Dynamics: Advances and Applications

In this contribution, we highlight the state of the art in the determination of structures with ultrafast electrons and X-rays. We provide our perspectives and reflections on the principles, techniques and methods, and on applications from different disciplines, with some focus on physical, chemical and biological structures. Although this article is not a survey of all the work done with these techniques, it provides a comprehensive referencing to current research.

Molecular Structural Dynamics Probed by Ultrafast X-Ray Absorption Spectroscopy

The ability to visualize molecular structure in the course of a chemical reaction or a biological function has been a dream of scientists for decades. X-ray absorption spectroscopy (XAS) is ideal in this respect because it is chemically selective and can be implemented in any type of medium. Furthermore, using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) in laser pump/X-ray probe experiments allows the retrieval of not only the local geometric structure of the system under study, but also the underlying electronic structure changes that drive the structural dynamics. We review recent developments in picosecond and femtosecond XAS applied to molecular systems in solution. Examples on ultrafast photoinduced processes such as intramolecular electron transfer, low-to-high spin change, and bond formation are presented.

Femtochemistry: Ultrafast Chemical and Physical Processes in Molecular Systems

This book highlights the latest experimental and theoretical developments in the field of femtochemistry, with papers describing the physics and chemistry of ultrafast processes in small molecules, complex molecular systems, clusters, biological systems, solids, matrices, liquids, and at surfaces and interfaces. In addition, the latest achievements in femtosecond control of chemical reactions are presented, together with the newest techniques in real-time probing of reactions such as ultrafast x-ray or electron diffraction.

Vibrational Coherences and Relaxation in the High‐Spin State of Aqueous [FeII(bpy)3]2+

Dizzy cooling: Femtosecond excitation of the singlet states of aqueous [FeII(bpy)3]2+ (bpy=2,2-bipyridine) leads to the formation of a vibrationally hot quintet state that exhibits wave-packet dynamics arising from a chelate-ring and bending mode. The vibrational relaxation involves at least two modes: the FeN stretching mode (see picture) and the coherently excited chelate-ring and bending mode, which relax on different time scales.

Fluorescence and Phosphorescence from Individual C60 Molecules Excited by Local Electron Tunneling

Using the highly localized current of electrons tunneling through a double barrier scanning tunneling microscope junction, we excite luminescence from a selected C60 molecule in the surface layer of fullerene nanocrystals grown on an ultrathin NaCl film on Au(111). In the observed fluorescence and phosphorescence spectra, pure electronic as well as vibronically induced transitions of an individual C60 molecule are identified, leading to unambiguous chemical recognition on the single-molecular scale.

Sub-50-fs photoinduced spin crossover in [Fe(bpy) 3 ] 2+

It is known that excitation by visible light of the singlet metal-to-ligand charge-transfer ((1)MLCT) states of Fe(II) complexes leads to population of the lowest-lying high-spin quintet state ((5)T) with unity quantum yield. Here we investigate this so-called spin crossover (SCO) transition in aqueous iron(II)tris(bipyridine). We use pump-probe transient absorption spectroscopy with a high time resolution of <60 fs in the ultraviolet probe range, in which the (5)T state absorbs, and of <40 fs in the visible probe range, in which both the hot MLCT state and the (5)T state absorb. Our results show that the (5)T state is impulsively populated in less than 50 fs, which is the time we measured for the depopulation of the MCLT manifold. We propose that non-totally-symmetric modes mediate the process, possibly high-frequency modes of the bipyridine (bpy) ligand. These results show that even though the SCO process in Fe(II) complexes represents a strongly spin-forbidden (ΔS = 2) two-electron transition, spin flipping occurs at near subvibrational times and is intertwined with the electron and structural dynamics of the system.

Ultrafast excited-state dynamics of rhenium(I) photosensitizers [Re(Cl)(CO)3(N,N)] and [Re(imidazole)(CO)3(N,N)]+: diimine effects.

Femto- to picosecond excited-state dynamics of the complexes [Re(L)(CO)(3)(N,N)](n) (N,N = bpy, phen, 4,7-dimethyl-phen (dmp); L = Cl, n = 0; L = imidazole, n = 1+) were investigated using fluorescence up-conversion, transient absorption in the 650-285 nm range (using broad-band UV probe pulses around 300 nm) and picosecond time-resolved IR (TRIR) spectroscopy in the region of CO stretching vibrations. Optically populated singlet charge-transfer (CT) state(s) undergo femtosecond intersystem crossing to at least two hot triplet states with a rate that is faster in Cl (∼100 fs)(-1) than in imidazole (∼150 fs)(-1) complexes but essentially independent of the N,N ligand. TRIR spectra indicate the presence of two long-lived triplet states that are populated simultaneously and equilibrate in a few picoseconds. The minor state accounts for less than 20% of the relaxed excited population. UV-vis transient spectra were assigned using open-shell time-dependent density functional theory calculations on the lowest triplet CT state. Visible excited-state absorption originates mostly from mixed L;N,N(•-) → Re(II) ligand-to-metal CT transitions. Excited bpy complexes show the characteristic sharp near-UV band (Cl, 373 nm; imH, 365 nm) due to two predominantly ππ*(bpy(•-)) transitions. For phen and dmp, the UV excited-state absorption occurs at ∼305 nm, originating from a series of mixed ππ* and Re → CO;N,N(•-) MLCT transitions. UV-vis transient absorption features exhibit small intensity- and band-shape changes occurring with several lifetimes in the 1-5 ps range, while TRIR bands show small intensity changes (≤5 ps) and shifts (∼1 and 6-10 ps) to higher wavenumbers. These spectral changes are attributable to convoluted electronic and vibrational relaxation steps and equilibration between the two lowest triplets. Still slower changes (≥15 ps), manifested mostly by the excited-state UV band, probably involve local-solvent restructuring. Implications of the observed excited-state behavior for the development and use of Re-based sensitizers and probes are discussed.

Temperature effects on the spectral properties of colloidal CdSe nanodots, nanorods, and tetrapods

The temperature dependence of the absorption and fluorescence spectra of colloidal CdSe nanocrystals was compared for three different shapes (dots, rods, and tetrapods) in the range of 4–300K. While the shift of the fluorescence maximum indicates little dependence on the shape, the authors find that the broadening of the emission spectrum behaves very differently for dots and rods, indicating major differences in the broadening mechanisms for different shapes. Tetrapods behave more similarly to dots, which suggests that the lowest exciton state is centered at the core.

A high-repetition rate scheme for synchrotron-based picosecond laser pump/x-ray probe experiments on chemical and biological systems in solution

We present the extension of time-resolved optical pump/x-ray absorption spectroscopy (XAS) probe experiments towards data collection at MHz repetition rates. The use of a high-power picosecond laser operating at an integer fraction of the repetition rate of the storage ring allows exploitation of up to two orders of magnitude more x-ray photons than in previous schemes based on the use of kHz lasers. Consequently, we demonstrate an order of magnitude increase in the signal-to-noise of time-resolved XAS of molecular systems in solution. This makes it possible to investigate highly dilute samples at concentrations approaching physiological conditions for biological systems. The simplicity and compactness of the scheme allows for straightforward implementation at any synchrotron beamline and for a wide range of x-ray probe techniques, such as time-resolved diffraction or x-ray emission studies.