Pasi Myllyperkiö

Photoinduced Ultrafast Dynamics of Ru(dcbpy)2(NCS)2-Sensitized Nanocrystalline TiO2 Films: The Influence of Sample Preparation and Experimental Conditions

In most of the previous ultrafast electron injection studies of Ru(dcbpy)2(NCS)2-sensitized nanocrystalline TiO2 films, experimental conditions and sample preparation have been different from study to study and no studies of how the differences affect the observed dynamics have been reported. In the present paper, we have investigated the influence of such modifications. Pump photon density, environment of the sensitized film (solvent and air), and parameters of the film preparation (crystallinity and quality of the film) were varied in a systematic way and the obtained dynamics were compared to that of a well-defined reference sample: Ru(dcbpy)2(NCS)2-TiO2 in acetonitrile. In some cases, the induced changes in the dynamics were uncorrelated to the electron injection process. High pump photon density (not in the linear response region) and exposure of the sensitized film to air altered the picosecond-time-scale kinetics considerably, and the changes were attributed mostly to degradation of the dye. In other cases, changes in the measured kinetics were related to the electron injection processes: reducing the firing temperature of the nanocrystalline film or making the film via electron beam evaporation (EBE) resulted in a decrease of the overall crystallinity of the film, and the electron injection slowed. In the sensitized EBE films, in addition to an increased contribution of triplet excited-state electron injection, a new electron transfer (ET) process with a time constant of 200 fs was observed.

Excitation Energy Transfer in Isolated Chlorosomes from Chlorobaculum tepidum and Prosthecochloris aestuarii

Excitation energy transfer in chlorosomes from photosynthetic green sulfur bacteria, Chlorobaculum (Cba.) tepidum and Prosthecochloris (Pst.) aestuarii, have been studied at room temperature by time‐resolved femtosecond transient absorption spectroscopy. Bleach rise times from 117 to 270 fs resolved for both chlorosomes reflect extremely efficient intrachlorosomal energy transfer. Bleach relaxation times, from 1 to 3 ps and 25 to 35 ps, probed at 758 nm were tentatively assigned to intrachlorosomal energy transfer based on amplitude changes of the global fits and model calculations. The anisotropy decay constant of about 1 ps resolved at 807 nm probe wavelength for the chlorosomes from Chloroflexus aurantiacus, Pst. aestuarii and Cba. tepidum was related to energy transfer between bacteriochlorophyll a molecules of the baseplate and partly to intrachlorosomal energy transfer. The longer anisotropy components 6.6, 8.8 and 12.1 ps resolved for the three chlorosomes, respectively, were assigned to chlorosome to baseplate energy transfer. Global fits of magic‐angle data also revealed longer chlorosome to baseplate energy transfer components from 95 to 135 ps, in accord with results from simulations.

Molecule-like photodynamics of Au102(pMBA)44 nanocluster.

Photophysical properties of a water-soluble cluster Au102(pMBA)44 (pMBA = para-mercaptobenzoic acid) are studied by ultrafast time-resolved mid-IR spectroscopy and density functional theory calculations in order to distinguish between molecular and metallic behavior. In the mid-IR transient absorption studies, visible or near-infrared light is used to electronically excite the sample, and the subsequent relaxation is monitored by studying the transient absorption of a vibrational mode in the ligands. Based on these studies, a complete picture of energy relaxation dynamics is obtained: (1) 0.5-1.5 ps electronic relaxation, (2) 6.8 ps vibrational cooling, (3) intersystem crossing from the lowest triplet state to the ground state with a time constant 84 ps, and (4) internal conversion to the ground state with a time constant of ∼3.5 ns. A remarkable finding based on this work is that a large cluster containing 102 metal atoms behaves like a small molecule in a striking contrast to a previously studied slightly larger Au144(SC2H4Ph)60 cluster, which shows relaxation typical for metallic particles. These results therefore establish that the transition between molecular and metallic behavior occurs between Au102 and Au144 species.

Time-resolved coherent anti-stokes raman-scattering measurements of I2 in solid Kr : Vibrational dephasing on the ground electronic state at 2.6-32 K

Time-resolved coherent anti-Stokes Raman-scattering (CARS) measurements are carried out for iodine (I2) in solid krypton matrices. The dependence of vibrational dephasing time on temperature and vibrational quantum number v is studied. The v dependence is approximately quadratic, while the temperature dependence of both vibrational dephasing and spectral shift, although weak, fits the exponential form characteristic of dephasing by pseudolocal phonons. The analysis of the data indicates that the frequency of the pseudolocal phonons is approximately 30 cm(-1). The longest dephasing times are observed for v = 2 being approximately 300 ps and limited by inhomogeneous broadening. An increase in the dephasing rate of v = 2 as the temperature is lowered to T = 2.6 K is taken as a clear indication of lattice-strain-induced inhomogeneity of the ensemble coherence.

Vibrational Relaxation of Matrix-Isolated Carboxylic Acid Dimers and Monomers †

Femtosecond mid-IR transient absorption spectroscopy was used to probe the vibrational dynamics of formic acid and acetic acid isolated in solid argon following excitation of the fundamental transition of the carbonyl stretching mode. Carboxylic acids form extremely stable H-bonded dimers, hindering the study of the monomeric species at equilibrium conditions. The low-temperature rare-gas matrix isolation technique allows for a unique control over aggregation enabling the study of the monomer vibrational dynamics, as well as the dynamics of two distinct dimer structures (cyclic and open chain). This study provides insight into the role of the methyl rotor and hydrogen bonding in the vibrational dynamics of carboxylic acids. In the monomer of FA, depopulation of the initially excited state is characterized by a time constant of approximately 500 ps, and it is followed by the energy transfer from intermediately populated intramolecular vibrational states into the phonon modes of the argon lattice (vibrational cooling) in a much longer time scale (estimated to be longer than 5 ns). The methyl rotor in acetic acid monomer accelerates both processes of population transfer and vibrational cooling, with time constants of approximately 80 ps. Hydrogen bonding in formic acid dimers decreases the time constant associated with the dominant vibrational relaxation process by more than 2 orders of magnitude. Unlike in formic acid, hydrogen bonding in acetic acid has no apparent effect on the vibrational cooling rate.

Femtosecond four-wave-mixing spectroscopy of suspended individual semiconducting single-walled carbon nanotubes.

Femtosecond four-wave-mixing (FWM) experiments of individual suspended semiconducting single-walled carbon nanotubes (SWCNTs) are presented. The chiral indices of the tubes were determined by electron diffraction as (28,14) and (24,14) having diameters of 2.90 and 2.61 nm, respectively. The diameter and semiconducting character of the tubes were additionally confirmed by resonance Raman measurements. The FWM signal showed electronic response from the SWCNTs. The results demonstrate that ultrafast dynamics of individual SWCNTs can be studied by FWM spectroscopies.

Photochemical reactivity of halogen-containing ruthenium–dcbpy (dcbpy = 4,4′-dicarboxylic acid-2,2′-bipyridine) compounds, trans(Br)-[Ru(dcbpy)(CO)2Br2] and trans(I)-[Ru(dcbpy)(CO)2I2]

The ruthenium mono(dcbpy) (dcbpy = 4,4′-dicarboxylic acid-2,2′-bipyridine) complexes, trans(Br)-[Ru(dcbpy)(CO)2Br2] and trans(I)-[Ru(dcbpy)(CO)2I2], have been synthesized and structurally characterized. Both compounds show strong photochemical activity. Under illumination in acetonitrile the colour of the dye solutions changes and infrared spectra indicate an irreversible change, with two CO stretching bands disappearing from the spectra with concomitant appearance of a new CO stretching band, an indication of a loss of a CO ligand. Changes in the proton NMR spectra suggest that the release of the CO ligand is followed by reorganization of the halogen ligands and attachment of one solvent molecule leading to formation of the cis(X)-Ru(dcbpy)(CO)(CH3CN)X2] (X = Br, I) isomer. In the visible spectra, a new absorption band appears under illumination at 510 nm allowing observation of the kinetics of the reaction. The quantum yields of the reactions are 0.68 and 0.34 for the bromine and iodine complexes, respectively. The trans(I)-[Ru(dcbpy)(CO)2I2] compound shows a temperature dependent luminescence spectrum in the temperature range 77 to 116 K, with an activation energy of 850 cm−1. We assign this dependence to a thermal population of a secondary triplet size, slightly above the emitting state, that is capable of initiating the photochemical reaction and/or a non-radiative relaxation to the ground state. The redox properties of the starting materials and the photoreaction products were studied with cyclic voltammetry and the results are discussed with reference to the reaction mechanisms.

Role of Vibrational Dynamics in Electronic Relaxation of Cr(acac)3

Ultrafast energy relaxation of Cr(acac)3 dissolved in tetrachloroethylene (TCE) is studied by time-resolved infrared (TRIR) spectroscopy by using electronic and vibrational excitation. After electronic excitation at 400 or 345 nm, the ground state recovers in two time scales: 15 ps (major pathway) and 800 ps (minor pathway), corresponding to fast electronic transition to the ground state and intermediate trapping on the long-lived (2)E state followed by intersystem crossing (ISC) to the ground state. The quantum yield for the fast recovery of the ground state depends on the excitation wavelength, being higher for 345 nm. Vibrational cooling (VC) occurs on the electronic excited states with a time constant of ∼7 ps and on the ground electronic state with a time constant of ∼12 ps. A kinetic model that explains the observed dynamics is presented. The key point of the model is that the ground-state recovery occurs via thermally activated back-intersystem-crossing (b-ISC) to the quartet manifold presumably via multiple curve crossings that are sampled while the system is vibrationally hot. This underlines the importance of vibrational cooling as a determining factor for the electronic relaxation chain. Vibrational excitation of the νC═C and νCO vibrations also revealed a subpicosecond (300-700 fs) intramolecular vibrational redistribution (IVR) process from the localized vibrational states to the bath of vibrational excitations.

Measurement of optical second-harmonic generation from an individual single-walled carbon nanotube

We show that optical second-harmonic generation (SHG) can be observed from individual single-walled carbon nanotubes (SWCNTs) and, furthermore, allows imaging of individual tubes. Detailed analysis of our results suggests that the structural non-centrosymmetry, as required for SHG, arises from the non-zero chiral angle of the SWCNT. SHG thus has potential as a fast, non-destructive and simple method for imaging of individual nanomolecules and for probing their chiral properties.

Real-time monitoring of graphene patterning with wide-field four-wave mixing microscopy

The single atom thick two-dimensional graphene is a promising material for various applications due to its extraordinary electronic, optical, optoelectronic, and mechanical properties. The demand for developing graphene based applications has entailed a requirement for development of methods for fast imaging techniques for graphene. Here, we demonstrate imaging of graphene with femtosecond wide-field four-wave mixing microscopy. The method provides a sensitive, non-destructive approach for rapid large area characterization of graphene. We show that the method is suitable for online following of a laser patterning process of microscale structures on single-layer graphene.