Vibrational coherences in half-broadband 2D electronic spectroscopy: Spectral filtering to identify excited state displacements.

Vibrational coherences in ultrafast pump-probe (PP) and 2D electronic spectroscopy (2DES) provide insights into the excited state dynamics of molecules. Femtosecond coherence spectra and 2D beat maps yield information about displacements of excited state surfaces for key vibrational modes. Half-broadband 2DES uses a PP configuration with a white light continuum probe to extend the detection range and resolve vibrational coherences in the excited state absorption (ESA). However, the interpretation of these spectra is difficult as they are strongly dependent on the spectrum of the pump laser and the relative displacement of the excited states along the vibrational coordinates. We demonstrate the impact of these convoluting factors for a model based upon cresyl violet. A careful consideration of the position of the pump spectrum can be a powerful tool in resolving the ESA coherences to gain insights into excited state displacements. This paper also highlights the need for caution in considering the spectral window of the pulse when interpreting these spectra.

Ultrafast and Coherent Dynamics in a Solvent Switchable "Pink Box" Perylene Diimide Dimer.

Perylene diimide (PDI) dimers and higher aggregates are key components in organic molecular photonics and photovoltaic devices, supporting singlet fission and symmetry breaking charge separation. Detailed understanding of their excited states is thus important. This has proven challenging because interchromophoric coupling is a strong function of dimer architecture. Recently, a macrocyclic PDI dimer was reported in which excitonic coupling could be turned on and off simply by changing the solvent. This presents a useful case where coupling is modified without synthetic changes to tune supramolecular structure. Here we present a detailed study of solvent dependent excited state dynamics in this dimer by means of coherent multidimensional spectroscopy. Spectral analysis resolves the different coupling strengths, which are consistent with solvent dependent changes in dimer conformation. The strongly coupled conformer forms an excimer within 300 fs. The low-frequency Raman active modes recovered from two-dimensional electronic spectra reveal frequencies characteristic of exciton coupling. These are assigned to modes modulating the coupling from the corresponding DFT calculations. Further analysis reveals a time dependent frequency during excimer formation. Analysis of two-dimensional "beatmaps" reveals features in the coupled dimer which are not predicted by the displaced harmonic oscillator model and are assigned to vibronic coupling.

Half-broadband two-dimensional electronic spectroscopy with active noise reduction.

Two-dimensional electronic spectroscopy (2DES) provides detailed insight into coherent ultrafast molecular dynamics in the condensed phase. Here we report a referenced broadband pump-compressed continuum probe half-broadband (HB) 2DES spectrometer in a partially collinear geometry. To optimize signal-to-noise ratio (SNR) we implement active noise reduction referencing, which has not previously been applied in 2DES. The method is calibrated against the well characterized 2DES response of the oxazine dye cresyl violet and demonstrated at visible wavelengths on the photochromic photoswitch 1,2-Bis(2-methyl-5-phenyl-3-thienyl) perfluorocyclopentene (DAE). The SNR is improved by a factor of ∼2 through active referencing. This is illustrated in an application to resolve a low frequency mode in the excited electronic state of DAE, yielding new data on the reaction coordinate. We show that the active noise reduction referencing, coupled with the rapid data collection, allows the extraction of weak vibronic features, most notably a low frequency mode in the excited electronic state of DAE.

Theory of two-dimensional spectroscopy with intense laser fields.

Two-dimensional vibrational and electronic spectroscopic observables of isotropically oriented molecular samples in solution are sensitive to laser field intensities and polarization. The third-order response function formalism predicts a signal that grows linearly with the field strength of each laser pulse, thus lacking a way of accounting for non-trivial intensity-dependent effects, such as saturation and finite bleaching. An analytical expression to describe the orientational part of the molecular response, which, in the weak-field limit, becomes equivalent to a four-point correlation function, is presented. Such an expression is evaluated for Liouville-space pathways accounting for diagonal and cross peaks for all-parallel and cross-polarized pulse sequences, in both the weak- and strong-field conditions, via truncation of a Taylor series expansion at different orders. The results obtained in the strong-field conditions suggest how a careful analysis of two-dimensional spectroscopic experimental data should include laser pulse intensity considerations when determining molecular internal coordinates.

Ultrafast Excimer Formation and Solvent Controlled Symmetry Breaking Charge Separation in the Excitonically Coupled Subphthalocyanine Dimer.

Knowledge of the factors controlling excited state dynamics in excitonically coupled dimers and higher aggregates is critical for understanding natural and artificial solar energy conversion. In this work, we report ultrafast solvent polarity dependent excited state dynamics of the structurally well-defined subphthalocyanine dimer, µ-OSubPc2 . Stationary electronic spectra demonstrate strong exciton coupling in µ-OSubPc2 . Femtosecond transient absorption measurements reveal ultrafast excimer formation from the initially excited exciton, mediated by intramolecular structural evolution. In polar solvents the excimer state decays directly through symmetry breaking charge transfer to form a charge separated state. Charge separation occurs under control of solvent orientational relaxation.

Ultrafast Excited State Dynamics in a First Generation Photomolecular Motor.

Efficient photomolecular motors will be critical elements in the design and development of molecular machines. Optimisation of the quantum yield for photoisomerisation requires a detailed understanding of molecular dynamics in the excited electronic state. Here we probe the primary photophysical processes in the archetypal first generation photomolecular motor, with sub-50 fs time resolved fluorescence spectroscopy. A bimodal relaxation is observed with a 100 fs relaxation of the Franck-Condon state to populate a red-shifted state with a reduced transition moment, which then undergoes multi-exponential decay on a picosecond timescale. Oscillations due to the excitation of vibrational coherences in the S1 state are seen to survive the ultrafast structural relaxation. The picosecond relaxation reveals a strong solvent friction effect which is thus ascribed to torsion about the C-C axle. This behaviour is contrasted with second generation photomolecular motors; the principal differences are explained by the existence of a barrier on the excited state surface in the case of the first-generation motors which is absent in the second generation. These results will help to provide a basis for designing more efficient molecular motors in the future.

Electronic Energy Transfer in a Subphthalocyanine-Zn Porphyrin Dimer Studied by Linear and Nonlinear Ultrafast Spectroscopy.

The efficient harvesting and transport of visible light by electronic energy transfer (EET) are critical to solar energy conversion in both nature and molecular electronics. In this work, we study EET in a synthetic dyad comprising a visible absorbing subphthalocyanine (SubPc) donor and a Zn tetraphenyl porphyrin (ZnTPP) acceptor. Energy transfer is probed by steady-state spectroscopy, ultrafast transient absorption, and two-dimensional electronic spectroscopy. Steady-state and time-resolved experiments point to only weak electronic coupling between the components of the dimer. The weak coupling supports energy transfer from the SubPc to the zinc porphyrin in 7 ps, which itself subsequently undergoes intersystem crossing to populate the triplet state. The rate of the forward energy transfer is discussed in terms of the structure of the dimer, which is calculated by density functional theory. There is evidence of back energy transfer from the ZnTPP on the hundreds of picoseconds time scale. Sub-picosecond spectral diffusion was also observed and characterized, but it does not influence the picosecond energy transfer.

One- to Two-Exciton Transitions in Perylene Bisimide Dimer Revealed by Two-Dimensional Electronic Spectroscopy.

The excited-state energy levels of molecular dimers and aggregates play a critical role in their photophysical behavior and an understanding of the photodynamics in such structures is important for developing applications such as photovoltaics and optoelectronic devices. Here, exciton transitions in two different covalently bound PBI dimers are studied by two-dimensional electronic spectroscopy (2DES), a powerful spectroscopic method, providing the most complete picture of vibronic transitions in molecular systems. The data are accurately reproduced using the equation of motion-phase matching approach. The unambiguous presence of one-exciton to two-exciton transitions are captured in our results and described in terms of a molecular exciton energy level scheme based on the Kasha model. Furthermore, the results are supported by comparative measurements with the PBI monomer and another dimer in which the interchromophore distance is increased.

Two-Dimensional Electronic Spectroscopy Resolves Relative Excited-State Displacements.

Knowledge of relative displacements between potential energy surfaces (PES) is critical in spectroscopy and photochemistry. Information on displacements is encoded in vibrational coherences. Here we apply ultrafast two-dimensional electronic spectroscopy in a pump-probe half-broadband (HB2DES) geometry to probe the ground- and excited-state potential landscapes of cresyl violet. 2D coherence maps reveal that while the coherence amplitude of the dominant 585 cm-1 Raman-active mode is mainly localized in the ground-state bleach and stimulated emission regions, a 338 cm-1 mode is enhanced in excited-state absorption. Modeling these data with a three-level displaced harmonic oscillator model using the hierarchical equation of motion-phase matching approach (HEOM-PMA) shows that the S1 ← S0 PES displacement is greater along the 585 cm-1 coordinate than the 338 cm-1 coordinate, while Sn ← S1 displacements are similar along both coordinates. HB2DES is thus a powerful tool for exploiting nuclear wavepackets to extract quantitative multidimensional, vibrational coordinate information across multiple PESs.

Photophysics of the red-form Kaede chromophore.

The green fluorescent protein (GFP) drove revolutionary progress in bioimaging. Photoconvertible fluorescent proteins (PCFPs) are an important branch of the FP family, of which Kaede is the prototype. Uniquely, PCFPs can be permanently switched from green to red emitting forms on UV irradiation, facilitating applications in site-specific photolabelling and protein tracking. Optimisation and exploitation of FPs requires understanding of the photophysical and photochemical behaviour of the chromophore. Accordingly, the principal GFP chromophore has been the subject of intense experimental and theoretical investigation. In contrast, the photophysics of the red emitting PCFP chromophore are largely unstudied. Here we present a detailed investigation of the excited-state properties of the Kaede chromophore in solution, utilising steady state measurements, ultrafast time-resolved electronic and vibrational spectroscopies, and electronic structure theory. Its excited state dynamics are very different to those of the parent GFP. Most remarkably, the PCFP chromophore has highly complex wavelength-dependent fluorescence decays and a mean lifetime an order of magnitude longer than the GFP chromophore. Transient electronic and vibrational spectroscopies suggest that these dynamics arise from a range of excited-state conformers that are spectrally and kinetically distinct but chemically similar. These conformers are populated directly by excitation of a broad thermal distribution of ground state structures about a single conformer, suggesting an excited-state potential surface with several minima. Temperature-dependence confirms the existence of barriers on the excited-state surface and reveals the radiationless decay mechanism to be internal conversion. These experimental observations are consistent with a model assuming a simple ground state potential energy surface accessing a complex excited state possessing multiple minima.

Population and coherence dynamics in large conjugated porphyrin nanorings.

In photosynthesis, nature exploits the distinctive electronic properties of chromophores arranged in supramolecular rings for efficient light harvesting. Among synthetic supramolecular cyclic structures, porphyrin nanorings have attracted considerable attention as they have a resemblance to naturally occurring light-harvesting structures but offer the ability to control ring size and the level of disorder. Here, broadband femtosecond transient absorption spectroscopy, with pump pulses in resonance with either the high or the low energy sides of the inhomogeneously broadened absorption spectrum, is used to study the population dynamics and ground and excited state vibrational coherence in large porphyrin nanorings. A series of fully conjugated, alkyne bridged, nanorings constituted of between ten and forty porphyrin units is studied. Pump-wavelength dependent fast spectral evolution is found. A fast rise or decay of the stimulated emission is found when large porphyrin nanorings are excited on, respectively, the high or low energy side of the absorption spectrum. Such dynamics are consistent with the hypothesis of a variation in transition dipole moment across the inhomogeneously broadened ground state ensemble. The observed dynamics indicate the interplay of nanoring conformation and oscillator strength. Oscillatory dynamics on the sub-ps time domain are observed in both pumping conditions. A combined analysis of the excitation wavelength-dependent transient spectra along with the amplitude and phase evolution of the oscillations allows assignment to vibrational wavepackets evolving on either ground or excited states electronic potential energy surfaces. Even though porphyrin nanorings support highly delocalized electronic wavefunctions, with coherence length spanning tens of chromophores, the measured vibrational coherences remain localised on the monomers. The main contributions to the beatings are assigned to two vibrational modes localised on the porphyrin cores: a Zn-N stretching mode and a skeletal methinic/pyrrolic C-C stretching and in-plane bending mode.