Figures of merit for mid-IR evanescent-wave absorption sensors and their simulation by FEM methods.

Proper optimization of a photonic structure for sensing applications is of extreme importance for integrated sensor design. Here we discuss on the definition of suitable parameters to determine the impact of photonic structure designs for evanescent-wave absorption sensors on the achievable resolution and sensitivity. In particular, we analyze the most widespread quantities used to classify photonic structures in the context of sensing, namely the evanescent-field ratio (or evanescent power factor) and the confinement factor Γ. We show that, somewhat counterintuitively, the confinement factor is the only parameter that can reliably describe the absorption of the evanescent-field in the surrounding medium, and, by quantifying the discrepancy between the two parameters for a set of realistic photonic structures, we demonstrate that using the evanescent-field ratio can lead to a wrong classification of the performance of different structures for absorption sensing. We finally discuss the most convenient simulation strategies to retrieve the confinement factor by FEM simulations.

Vibrational coherence transfer in the ultrafast intersystem crossing of a diplatinum complex in solution.

We investigate the ultrafast transient absorption response of tetrakis(µ-pyrophosphito)diplatinate(II), [Pt2(µ-P2O5H2)4]4- [hereafter abbreviated Pt(pop)], in acetonitrile upon excitation of its lowest singlet 1A2u state. Compared with previously reported solvents [van der Veen RM, Cannizzo A, van Mourik F, Vlcek A, Jr, Chergui M (2011) J Am Chem Soc 133:305-315], a significant shortening of the intersystem crossing (ISC) time (<1 ps) from the lowest singlet to the lowest triplet state is found, allowing for a transfer of vibrational coherence, observed in the course of an ISC in a polyatomic molecule in solution. Density functional theory (DFT) quantum mechanical/molecular mechanical (QM/MM) simulations of Pt(pop) in acetonitrile and ethanol show that high-lying, mostly triplet, states are strongly mixed and shifted to lower energies due to interactions with the solvent, providing an intermediate state (or manifold of states) for the ISC. This suggests that the larger the solvation energies of the intermediate state(s), the shorter the ISC time. Because the latter is smaller than the pure dephasing time of the vibrational wave packet, coherence is conserved during the spin transition. These results underscore the crucial role of the solvent in directing pathways of intramolecular energy flow.

Tryptophan-to-heme electron transfer in ferrous myoglobins.

It was recently demonstrated that in ferric myoglobins (Mb) the fluorescence quenching of the photoexcited tryptophan 14 (*Trp(14)) residue is in part due to an electron transfer to the heme porphyrin (porph), turning it to the ferrous state. However, the invariance of *Trp decay times in ferric and ferrous Mbs raises the question as to whether electron transfer may also be operative in the latter. Using UV pump/visible probe transient absorption, we show that this is indeed the case for deoxy-Mb. We observe that the reduction generates (with a yield of about 30%) a low-valence Fe-porphyrin π [Fe(II)(porph(●-))] -anion radical, which we observe for the first time to our knowledge under physiological conditions. We suggest that the pathway for the electron transfer proceeds via the leucine 69 (Leu(69)) and valine 68 (Val(68)) residues. The results on ferric Mbs and the present ones highlight the generality of Trp-porphyrin electron transfer in heme proteins.

Interfacial Electron Injection Probed by a Substrate-Specific Excitonic Signature.

Ultrafast interfacial electron transfer in sensitized solar cells has mostly been probed by visible-to-terahertz radiation, which is sensitive to the free carriers in the conduction band of the semiconductor substrate. Here, we demonstrate the use of deep-ultraviolet continuum pulses to probe the interfacial electron transfer, by detecting a specific excitonic transition in both N719-sensitized anatase TiO2 and wurtzite ZnO nanoparticles. Our results are compared to those obtained on bare nanoparticles upon above-gap excitation. We show that the signal upon electron injection from the N719 dye into TiO2 is dominated by long-range Coulomb screening of the final states of the excitonic transitions, whereas in sensitized ZnO it is dominated by phase-space filling. The present approach offers a possible route to detecting interfacial electron transfer in a broad class of systems, including other transition metal oxides or sensitizers.

Photoaquation Mechanism of Hexacyanoferrate(II) Ions: Ultrafast 2D UV and Transient Visible and IR Spectroscopies.

Ferrous iron(II) hexacyanide in aqueous solutions is known to undergo photoionization and photoaquation reactions depending on the excitation wavelength. To investigate this wavelength dependence, we implemented ultrafast two-dimensional UV transient absorption spectroscopy, covering a range from 280 to 370 nm in both excitation and probing, along with UV pump/visible probe or time-resolved infrared (TRIR) transient absorption spectroscopy and density functional theory (DFT) calculations. As far as photoaquation is concerned, we find that excitation of the molecule leads to ultrafast intramolecular relaxation to the lowest triplet state of the [Fe(CN)6]4- complex, followed by its dissociation into CN- and [Fe(CN)5]3- fragments and partial geminate recombination, all within <0.5 ps. The subsequent time evolution is associated with the [Fe(CN)5]3- fragment going from a triplet square pyramidal geometry, to the lowest triplet trigonal bipyramidal state in 3-4 ps. This is the precursor to aquation, which occurs in ∼20 ps in H2O and D2O solutions, forming the [Fe(CN)5(H2O/D2O)]3- species, although some aquation also occurs during the 3-4 ps time scale. The aquated complex is observed to be stable up to the microsecond time scale. For excitation below 310 nm, the dominant channel is photooxidation with a minor aquation channel. The photoaquation reaction shows no excitation wavelength dependence up to 310 nm, that is, it reflects a Kasha Rule behavior. In contrast, the photooxidation yield increases with decreasing excitation wavelength. The various intermediates that appear in the TRIR experiments are identified with the help of DFT calculations. These results provide a clear example of the energy dependence of various reactive pathways and of the role of spin-states in the reactivity of metal complexes.

A cascade through spin states in the ultrafast haem relaxation of met-myoglobin.

We report on a study of the early relaxation processes of met-Myoglobin in aqueous solution, using a combination of ultrafast broadband fluorescence detection and transient absorption with a broad UV-visible continuum probe at different pump energies. Reconstruction of the spectra of the transient species unravels the details of the haem photocycle in the absence of photolysis. Besides identifying a branching in the ultrafast relaxation of the haem, we show clear evidence for an electronic character of the intermediates, contrary to the commonly accepted idea that the early time relaxation of the haem is only due to cooling. The decay back to the ground state proceeds partially as a cascade through iron spin states, which seems to be a general characteristic of haem systems.

Ultrabroadband femtosecond two-dimensional ultraviolet transient absorption.

We present a broadband two-dimensional transient absorption setup for the UV around 300 nm with a time resolution of 150 fs. A narrowband, frequency tunable pump pulse and a broadband probe pulse are generated from the output of a noncollinear optical parametric amplifier operated at 20 kHz repetition rate and combined in a spectrally resolved transient absorption experiment. The high repetition rate and low noise of the setup allow us to acquire high quality two-dimensional data as a function of time delay with an unsurpassed frequency window of 10,000 and 8000 cm(-1) along the probe and pump axis, respectively. The performance of the setup is demonstrated on 2,5-Diphenyloxazol dissolved in cyclohexane.

Ultrafast (bio)physical and (bio)chemical dynamics.

We give an overview of our recent work on ultrafast dynamics of chemical (organic dyes, metal-complexes, colloidal quantum dots), and biological (retinal and haem proteins) systems in the liquid phase, studied with a variety of ultrafast optical techniques from the infrared to the ultraviolet.

Relativistic Jahn-Teller effects in the quartet states of K3 and Rb3: a vibronic analysis of the 2 (4)E' <-- 1 (4)A2' electronic transitions based on ab initio calculations.

We apply second-order multireference Rayleigh-Schrodinger perturbation theory to obtain the adiabatic potential energy surface of the 1 (4)A(2)(') lowest quartet state and the 2 (4)E(') excited state of K(3) and Rb(3). Both trimers show a typical Emultiply sign in circlee Jahn-Teller distortion in their 2 (4)E(') state, which is analyzed in terms of relativistic Jahn-Teller effect theory. Linear, quadratic, and spin-orbit coupling terms are extracted from the ab initio results and used to generate simulated spectra for a direct comparison with laser-induced fluorescence and magnetic circular dichroism spectra of alkali-doped helium nanodroplets [Aubock et al., J. Chem. Phys. 129, 114501 (2008)].

One- and two-photon spectroscopy of highly excited states of alkali-metal atoms on helium nanodroplets.

Alkali-metal atoms captured on the surface of superfluid helium droplets are excited to high energies (≈3 eV) by means of pulsed lasers, and their laser-induced-fluorescence spectra are recorded. We report on the one-photon excitation of the (n+1)p←ns transition of K, Rb, and Cs (n=4, 5, and 6, respectively) and on the two-photon one-color excitation of the 5d←5s transition of Rb. Gated-photon-counting measurements are consistent with the relaxation rates of the bare atoms, hence consistent with the reasonable expectation that atoms quickly desorb from the droplet and droplet-induced relaxation need not be invoked.

Wafer-Level Vacuum-Packaged Translatory MEMS Actuator with Large Stroke for NIR-FT Spectrometers.

We present a wafer-level vacuum-packaged (WLVP) translatory micro-electro-mechanical system (MEMS) actuator developed for a compact near-infrared-Fourier transform spectrometer (NIR-FTS) with 800-2500 nm spectral bandwidth and signal-nose-ratio (SNR) > 1000 in the smaller bandwidth range (1200-2500 nm) for 1 s measuring time. Although monolithic, highly miniaturized MEMS NIR-FTSs exist today, we follow a classical optical FT instrumentation using a resonant MEMS mirror of 5 mm diameter with precise out-of-plane translatory oscillation for optical path-length modulation. Compared to highly miniaturized MEMS NIR-FTS, the present concept features higher optical throughput and resolution, as well as mechanical robustness and insensitivity to vibration and mechanical shock, compared to conventional FTS mirror drives. The large-stroke MEMS design uses a fully symmetrical four-pantograph suspension, avoiding problems with tilting and parasitic modes. Due to significant gas damping, a permanent vacuum of ≤3.21 Pa is required. Therefore, an MEMS design with WLVP optimization for the NIR spectral range with minimized static and dynamic mirror deformation of ≤100 nm was developed. For hermetic sealing, glass-frit bonding at elevated process temperatures of 430-440 °C was used to ensure compatibility with a qualified MEMS processes. Finally, a WLVP MEMS with a vacuum pressure of ≤0.15 Pa and Q ≥ 38,600 was realized, resulting in a stroke of 700 µm at 267 Hz for driving at 4 V in parametric resonance. The long-term stability of the 0.2 Pa interior vacuum was successfully tested using a Ne fine-leakage test and resulted in an estimated lifetime of >10 years. This meets the requirements of a compact NIR-FTS.

Sub-50-fs photoinduced spin crossover in [Fe(bpy)3]²âº.

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 tryptophan-to-heme electron transfer in myoglobins revealed by UV 2D spectroscopy.

Tryptophan is commonly used to study protein structure and dynamics, such as protein folding, as a donor in fluorescence resonant energy transfer (FRET) studies. By using ultra-broadband ultrafast two-dimensional (2D) spectroscopy in the ultraviolet (UV) and transient absorption in the visible range, we have disentangled the excited state decay pathways of the tryptophan amino acid residues in ferric myoglobins (MbCN and metMb). Whereas the more distant tryptophan (Trp(7)) relaxes by energy transfer to the heme, Trp(14) excitation predominantly decays by electron transfer to the heme. The excited Trp(14)→heme electron transfer occurs in <40 picoseconds with a quantum yield of more than 60%, over an edge-to-edge distance below ~10 angstroms, outcompeting the FRET process. Our results raise the question of whether such electron transfer pathways occur in a larger class of proteins.

Femtosecond pump/supercontinuum-probe setup with 20 kHz repetition rate.

We developed a fast multichannel detection system for pump-probe spectroscopy, capable of detecting single shot super-continuum spectra at the repetition rate (10-50 kHz) of an amplified femtosecond laser system. By tandem pumping the amplifier with three pump lasers we obtain very low noise operation, with less than 0.1% rms intensity fluctuations at the output of the amplifier. We also propose an alternative way of chopping the pump beam. With a synchronized scanning mirror two spots in the sample are illuminated by the train of pump pulses in an alternating fashion, such that when both spots are interrogated by the probe pulse, the duty cycle of the experiment is doubled.

Multiphoton-excited luminescent lanthanide bioprobes: two- and three-photon cross sections of dipicolinate derivatives and binuclear helicates.

Multiphoton excited luminescent properties of water-soluble Eu(III) and Tb(III) complexes with derivatives of dipicolinic acid functionalized with a polyoxyethylene pendant arm and terminal groups, [Eu(L(OMe))(3)](3-), [Eu(L(NH2))(3)](3-), and [Tb(L(OH))(3)](3-), as well as of binuclear helicates with overall composition [Ln(2)(L(CX))(3)] (X = 2, 5) are investigated. Characteristic emission from the (5)D(0) and (5)D(4) excited levels of Eu(III) and Tb(III), respectively, upon approximately 800 nm excitation results from three-photon absorption (3PA) for [Eu(L(OMe))(3)](3-), [Eu(L(NH2))(3)](3-), [Tb(L(OH))(3)](3-), and [Ln(2)(L(C2))(3)], while luminescence from [Eu(2)(L(C5))(3)] is induced by two-photon absorption (2PA) owing to its 1PA spectrum extending further into the visible. The 3PA cross sections have been determined and are the first ones reported for lanthanide complexes: (i) those of Eu(III) and Tb(III) bimetallic helicates [Ln(2)(L(C2))(3)] are 20 times larger compared to the corresponding values for tris(dipicolinates); (ii) derivatization of dipicolinic acid for Tb(III) complexes has almost no influence on the 3PA cross section; however, for Eu(III) complexes a approximately 2 times decrease is observed. The feasibility of [Eu(2)(L(C5))(3)] as multiphoton luminescence bioprobe is demonstrated by two-photon scanning microscopy imaging experiments on HeLa cells incubated with this bimetallic helicate.

Coherent spin manipulation and ESR on superfluid helium nanodroplets.

Superfluid helium nanodroplets provide a versatile substrate to cool atoms and molecules, and to assemble weakly bound complexes. Absence of spin-relaxation mechanisms makes He nanodroplets ideal to isolate open-shell atoms and create a spin-polarized system. Here, we show the first coherent manipulation of such a system by resonant excitation of a magnetic-dipole transition. Observation of approximately 50 Rabi oscillations demonstrates coherent population transfer with minimal dephasing. Ours is also the first application of ESR spectroscopy to doped He nanodroplets. This unique environment results in extremely sharp lines and hyperfine-resolved spectra: those of single 39K and 85Rb dopant atoms presented here denote an increase of the Fermi contact interaction, which we can follow as a function of droplet size, reflecting the distortion of the valence-electron wave function due to the surrounding He.

Electron spin pumping of Rb atoms on He nanodroplets via nondestructive optical excitation.

We measured laser-induced-fluorescence (LIF) and beam-depletion (BD) spectra of rubidium atoms (5S-5P transition) on the surface of superfluid helium nanodroplets (M-He_{N} with M=Rb). It is known that when M is a lighter alkali atom electronic excitation always leads to detachment of the excited atom (M;{*}). The dissociation energy, few tens cm;{-1}, comes either as photon excess energy or from the barrierless formation of a M;{*}-He exciplex. We observe that this picture does not hold when M=Rb and the photon excess energy is small: we are able to excite atoms without detaching them from the droplet, thanks to a barrier preventing formation of the exciplex. This system is ideally suited for optical spin pumping in a He nanodroplet, whose achievement we explicitly demonstrate in a pump-probe magnetic circular dichroism experiment.

Heteronuclear and homonuclear high-spin alkali trimers on helium nanodroplets.

The electronic excitation spectra of all possible homo- and heteronuclear high-spin (quartet) trimers of K and Rb (KxRb(3-x), x=0...3) assembled on the surface of superfluid helium droplets, are measured in the spectral range from 10,600 to 17,400 cm(-1). A regular series of corresponding bands is observed, reflecting the similar electronic structure of all these trimers. For the assignment and separation of overlapping bands, we determine x directly, with mass-selected beam depletion, and indirectly with a V-type double-resonance scheme. The assignment is confirmed by high-level ab initio calculations of the electronic structure of the bare trimers. The level structure is rationalized in terms of harmonic-oscillator states of the three valence electrons in a quantum-dot-like confining potential. We predict that three should be a magic number for high-spin alkali clusters.

High-spin alkali trimers on helium nanodroplets: spectral separation and analysis.

Electronic excitation spectra of homo- (K(3),Rb(3)) and heteronuclear (K(2)Rb,KRb(2)) alkali trimers in the high-spin quartet state have been investigated in a broad spectral range (10,600-17,400 cm(-1)). Ten new bands showing laser induced fluorescence (LIF) were measured. Due to the pickup statistics, overlapping spectra of all possible oligomers are present at once, complicating the unraveling and assignment of individual spectra. To circumvent the problem, two variations of beam depletion spectroscopy were employed in addition to the conventional analysis of the relation between signal and pickup pressure: A two-laser V-type double resonance scheme combining beam depletion with LIF, and a mass selective beam depletion scheme. In principle, these allow accurate separation of an arbitrary number of overlapping spectra. The benefits and drawbacks of each method are discussed. Assignment to electronic states is achieved by comparison with ab initio complete active space self-consistent field calculations of the excited electronic level structure of the molecules.

Magnetic dichroism of potassium atoms on the surface of helium nanodroplets.

The population ratio of Zeeman sublevels of atoms on the surface of superfluid helium droplets (T=0.37 K) has been measured. Laser induced fluorescence spectra of K atoms are measured in the presence of a moderately strong magnetic field (2.9 kG). The relative difference between the two states of circular polarization of the exciting laser is used to determine the electron spin polarization of the ensemble. Equal fluorescence levels indicate that the two spin sublevels of the ground-state K atom are equipopulated, within 1%. Thermalization to 0.37 K would give a population ratio of 0.35. We deduce that the rate of spin relaxation induced by the droplet must be <520/s. For the K2 triplet dimer we find instead full thermalization of the spin.