Time resolved structural dynamics of butadiyne-linked porphyrin dimers

In this work the timescales and mechanisms associated with the structural dynamics of butadiyne-linked porphyrin dimers are investigated through time resolved narrowband pump / broadband probe transient absorption spectroscopy. Our results confirm previous findings that the broadening is partly due to a distribution of structures with different (dihedral) angular conformations. Comparison of measurements with excitations on the red and blue sides of the Q-band unravel the ground and excited state conformational re-equilibration timescales. Further comparison to a planarized dimer, through addition of a ligand, provide conclusive evidence for the twisting motion performed by the porphyrin dimer in solution

Spectral Filtering as a Tool for Two-Dimensional Spectroscopy: A Theoretical Model

Two-dimensional optical spectroscopy is a powerful technique for the probing of coherent quantum superpositions. Recently, the finite width of the laser spectrum has been employed to selectively tune experiments for the study of particular coherences. This involves the exclusion of certain transition frequencies, which results in the elimination of specific Liouville pathways. The rigorous analysis of such experiments requires the use of ever more sophisticated theoretical models for the optical spectroscopy of electronic and vibronic systems. Here we develop a non-impulsive and non-Markovian model which combines an explicit definition of the laser spectrum, via the equation of motion-phase matching approach (EOM-PMA), with the hierarchical equations of motion (HEOM). This theoretical framework is capable of simulating the 2D spectroscopy of vibronic systems with low frequency modes, coupled to environments of intermediate and slower timescales. In order to demonstrate the spectral filtering of vibronic coherences, we examine the elimination of lower energy peaks fromthe 2D spectra of a zinc porphyrin monomer on blue-shifting the laser spectrum. The filtering of Liouville pathways is revealed through the disappearance of peaks from the amplitude spectra for a coupled vibrational mode

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

Raman vibrational dynamics of hydrated ions in the low-frequency spectral region

The hydration structure of ions in aqueous environments can have a significant influence on their chemical and biological properties. Due to its inherent dynamical character, determination of the hydration shell around dissolved ions has proved challenging, mainly so for cations such as sodium and potassium which form diffuse and dynamic hydrating structures. The low frequency polarized Raman spectrum, as retrieved by time resolved isotropic optical Kerr effect measurements, is sensitive to structural fluctuations and can reveal information about ion-water interactions through their Raman active vibrational modes. Here we study a series of mixtures of sodium, potassium and lithium hydroxide solutions by changing cation concentration pairwise (namely, sodium/potassium or sodium/lithium) while keeping constant the hydroxide concentration. The hydroxide-water hydrogen bond vibration, which produces a well-defined isotropic Raman mode, appears at higher frequencies from the cation-water Raman active vibrations. In addition to previously reported lithium-water low frequency vibrations, clear spectral features could be resolved from the concentration studies and assigned to sodium-water hydration shell vibrations. However, potassium related low frequency spectral features remain elusive. The same method was applied to mixtures of the same cations with a halide anion (chloride) in order to rule out any specific features related to the dissolved hydroxide anion. Comparison between halide and hydroxide measurements confirmed the presence of the cation modes and further revealed a low frequency spectral feature related to hydroxide induced changes in water polarizability

Resolving vibrational from electronic coherences in two-dimensional electronic spectroscopy: The role of the laser spectrum

The observation of coherent quantum effects in photosynthetic light-harvesting complexes prompted the question whether quantum coherence could be exploited to improve the efficiency in new energy materials. The detailed characterization of coherent effects relies on sensitive methods such as two-dimensional electronic spectroscopy (2D-ES). However, the interpretation of the results produced by 2D-ES is challenging due to the many possible couplings present in complex molecular structures. In this work, we demonstrate how the laser spectral profile can induce electronic coherence-like signals in monomeric chromophores, potentially leading to data misinterpretation. We argue that the laser spectrum acts as a filter for certain coherence pathways and thus propose a general method to differentiate vibrational from electronic coherences

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

Ultrafast dynamics in light-driven molecular rotary motors probed by femtosecond stimulated raman spectroscopy

Photochemical isomerization in sterically crowded chiral alkenes is the driving force for molecular rotary motors in nanoscale machines. Here the excited state dynamics and structural evolution of the prototypical light driven rotary motor are followed on the ultrafast timescale by femtosecond stimulated Raman spectroscopy (FSRS) and transient absorption (TA). TA reveals a sub 100 fs blue shift and decay of the Franck-Condon bright state arising from relaxation along the reactive potential energy surface. The decay is accompanied by coherently excited vibrational dynamics which survive the excited state structural evolution. The ultrafast Franck-Condon bright state relaxation is to a dark excited state, which FSRS reveals to have a rich spectrum compared to the electronic ground state, with the most intense Raman active modes shifted to significantly lower wavenumber. This is discussed in terms of a reduced bond order of the central bridging bond and overall weakening of bonds in the dark state, which is supported by electronic structure calculations. The observed evolution in the FSRS spectrum is assigned to vibrational cooling accompanied by partitioning of the dark state between the product isomer and the original ground state. Formation of the product isomer is observed in real time by FSRS. It is formed vibrationally hot and cools over several picoseconds, completing the characterization of the light driven half of the photocycle

Exciton-Exciton Annihilation as a Probe of Exciton Diffusion in Large Porphyrin Nanorings

The photophysical behavior of natural and artificial cyclic supramolecular structures has been intensively investigated in the past decade. Among the artificial structures, large fully π-conjugated porphyrin nanorings are of particular interest because of their electronic, structural, and topological features, which make them suitable candidates for light-harvesting applications. A number of factors affect the efficiency with which such structures harvest and transmit energy. For instance, under intense irradiation conditions, the efficiency of light harvesting can be quenched by competing processes, such as exciton–exciton annihilation. Here, we investigate the pump fluence dependence of the transient absorption spectra of a series of porphyrin nanorings ranging in circumference between 13 and 52 nm (10–40 porphyrin units). This allowed the isolation of a fluence-dependent fast-decaying component in all but the smallest nanorings studied. This effect has been assigned to exciton–exciton annihilation and fit to a one-dimensional exciton diffusion model, which confirms that the exciton size and/or its mobility are inversely proportional to the nanoring size