Modulating Singlet Fission by Scanning through Vibronic Resonances in Pentacene-Based Blends.

Vibronic coupling has been proposed to play a decisive role in promoting ultrafast singlet fission (SF), the conversion of a singlet exciton into two triplet excitons. Its inherent complexity is challenging to explore, both from a theoretical and an experimental point of view, due to the variety of potentially relevant vibrational modes. Here, we report a study on blends of the prototypical SF chromophore pentacene in which we engineer the polarizability of the molecular environment to scan the energy of the excited singlet state (S1) continuously over a narrow energy range, covering vibrational sublevels of the triplet-pair state (1(TT)). Using femtosecond transient absorption spectroscopy, we probe the dependence of the SF rate on energetic resonance between vibronic states and, by comparison with simulation, identify vibrational modes near 1150 cm-1 as key in facilitating ultrafast SF in pentacene.

IR Spectroscopy Can Reveal the Mechanism of K+ Transport in Ion Channels.

Ion channels like KcsA enable ions to move across cell membranes at near diffusion-limited rates and with very high selectivity. Various mechanisms have been proposed to explain this phenomenon. Broadly, there is disagreement among the proposed mechanisms about whether ions occupy adjacent sites in the channel during the transport process. Here, using a mixed quantum-classical approach to calculate theoretical infrared spectra, we propose a set of infrared spectroscopy experiments that can discriminate between mechanisms with and without adjacent ions. These experiments differ from previous ones in that they independently probe specific ion binding sites within the selectivity filter. When ions occupy adjacent sites in the selectivity filter, the predicted spectra are significantly redshifted relative to when ions do not occupy adjacent sites. Comparisons between theoretical and experimental peak frequencies will therefore discriminate the mechanisms.

Expanded Theory of H- and J-Molecular Aggregates: The Effects of Vibronic Coupling and Intermolecular Charge Transfer.

The electronic excited states of molecular aggregates and their photophysical signatures have long fascinated spectroscopists and theoreticians alike since the advent of Frenkel exciton theory almost 90 years ago. The influence of molecular packing on basic optical probes like absorption and photoluminescence was originally worked out by Kasha for aggregates dominated by Coulombic intermolecular interactions, eventually leading to the classification of J- and H-aggregates. This review outlines advances made in understanding the relationship between aggregate structure and photophysics when vibronic coupling and intermolecular charge transfer are incorporated. An assortment of packing geometries is considered from the humble molecular dimer to more exotic structures including linear and bent aggregates, two-dimensional herringbone and "HJ" aggregates, and chiral aggregates. The interplay between long-range Coulomb coupling and short-range charge-transfer-mediated coupling strongly depends on the aggregate architecture leading to a wide array of photophysical behaviors.

Modeling nonlocal electron-phonon coupling in organic crystals using interpolative maps: The spectroscopy of crystalline pentacene and 7,8,15,16-tetraazaterrylene.

Electron-phonon coupling plays a central role in the transport properties and photophysics of organic crystals. Successful models describing charge- and energy-transport in these systems routinely include these effects. Most models for describing photophysics, on the other hand, only incorporate local electron-phonon coupling to intramolecular vibrational modes, while nonlocal electron-phonon coupling is neglected. One might expect nonlocal coupling to have an important effect on the photophysics of organic crystals because it gives rise to large fluctuation in the charge-transfer couplings, and charge-transfer couplings play an important role in the spectroscopy of many organic crystals. Here, we study the effects of nonlocal coupling on the absorption spectrum of crystalline pentacene and 7,8,15,16-tetraazaterrylene. To this end, we develop a new mixed quantum-classical approach for including nonlocal coupling into spectroscopic and transport models for organic crystals. Importantly, our approach does not assume that the nonlocal coupling is linear, in contrast to most modern charge-transport models. We find that the nonlocal coupling broadens the absorption spectrum non-uniformly across the absorption line shape. In pentacene, for example, our model predicts that the lower Davydov component broadens considerably more than the upper Davydov component, explaining the origin of this experimental observation for the first time. By studying a simple dimer model, we are able to attribute this selective broadening to correlations between the fluctuations of the charge-transfer couplings. Overall, our method incorporates nonlocal electron-phonon coupling into spectroscopic and transport models with computational efficiency, generalizability to a wide range of organic crystals, and without any assumption of linearity.

Mid-IR spectroscopy of supercritical water: From dilute gas to dense fluid.

Mixed quantum-classical methods are commonly used to calculate infrared spectra for condensed-phase systems. These methods have been applied to study water in a range of conditions from liquid to solid to supercooled. Here, we show that these methods also predict infrared line shapes in excellent agreement with experiments in supercritical water. Specifically, we study the OD stretching mode of dilute HOD in H2O. We find no qualitative change in the spectrum upon passing through the near-critical region (Widom line) or the hydrogen-bond percolation line. At very low densities, the spectrum does change qualitatively, becoming rovibrational in character. We describe this rovibrational spectrum from the perspective of classical mechanics and provide a classical interpretation of the rovibrational line shape for both HOD and H2O. This treatment is perhaps more accessible than the conventional quantum-mechanical treatment.

Molecular Aggregate Photophysics beyond the Kasha Model: Novel Design Principles for Organic Materials.

The transport and photophysical properties of organic molecular aggregates, films, and crystals continue to receive widespread attention, driven mainly by expanding commercial applications involving display and wearable technologies as well as the promise of efficient, large-area solar cells. The main blueprint for understanding how molecular packing impacts photophysical properties was drafted over five decades ago by Michael Kasha. Kasha showed that the Coulombic coupling between two molecules, as determined by the alignment of their transition dipoles, induces energetic shifts in the main absorption spectral peak and changes in the radiative decay rate when compared to uncoupled molecules. In H-aggregates, the transition dipole moments align "side-by-side" leading to a spectral blue-shift and suppressed radiative decay rate, while in J-aggregates, the transition dipole moments align "head-to-tail" leading to a spectral red-shift and an enhanced radiative decay rate. Although many examples of H- and J-aggregates have been discovered, there are also many "unconventional" aggregates, which are not understood within the confines of Kasha's theory. Examples include nanopillars of 7,8,15,16-tetraazaterrylene, as well as several perylene-based dyes, which exhibit so-called H- to J-aggregate transformations. Such aggregates are typically characterized by significant wave function overlap between neighboring molecular orbitals as a result of small (∼4 Å) intermolecular distances, such as those found in rylene π-stacks and oligoacene herringbone lattices. Wave function overlap facilitates charge-transfer which creates an effective short-range exciton coupling that can also induce J- or H-aggregate behavior, depending on the sign. Unlike Coulomb coupling, short-range coupling is extremely sensitive to small (sub-Å) transverse displacements between neighboring chromophores. For perylene chromophores, the sign of the short-range coupling changes several times as two molecules are "slipped" from a "side-by-side" to "head-to-tail" configuration, in marked contrast to the sign of the Coulomb coupling, which changes only once. Such sensitivity allows J- to H-aggregate interconversions over distances several times smaller than those predicted by Kasha's theory. Moreover, since the total coupling drives exciton transport and photophysical properties, interference between the short- and long-range (Coulomb) couplings, as manifest by their relative signs and magnitudes, gives rise to a host of new aggregate types, referred to as HH, HJ, JH, and JJ aggregates, with distinct photophysical properties. An extreme example is the "null" HJ-aggregate in which total destructive interference leads to absorption line shapes practically identical to uncoupled molecules. Moreover, the severely compromised exciton bandwidth effectively shuts down energy transport. Most importantly, the new aggregates types described herein can be exploited for electronic materials design. For example, the enhanced exciton bandwidth and weakly emissive properties of HH-aggregates make them ideal candidates for solar cell absorbers, while the enhanced charge mobility and strong emissive behavior of JJ-aggregates makes them excellent candidates for light-emitting diodes.

Perspective: Crossing the Widom line in no man's land: Experiments, simulations, and the location of the liquid-liquid critical point in supercooled water.

The origin of liquid water's anomalous behavior continues to be a subject of interest and debate. One possible explanation is the liquid-liquid critical point hypothesis, which proposes that supercooled water separates into two distinct liquids at low temperatures and high pressures. According to this hypothesis, liquid water's anomalies can be traced back to the critical point associated with this phase separation. If such a critical point actually exists, it is located in a region of the phase diagram known as No Man's Land (NML), where it is difficult to characterize the liquid using conventional experimental techniques due to rapid crystallization. Recently, however, experimentalists have managed to explore NML near the proposed location of the Widom line (i.e., the Kanno-Angell line), thereby providing valuable information concerning the liquid-liquid critical point hypothesis. In this perspective, we analyze these experimental results, in conjunction with molecular dynamics simulations based on the E3B3 water model and discuss their implications for the validity of the liquid-liquid critical point hypothesis and the possible location of water's second critical point.

Communication: Diffusion constant in supercooled water as the Widom line is crossed in no man's land.

According to the liquid-liquid critical point (LLCP) hypothesis, there are two distinct phases of supercooled liquid water, namely, high-density liquid and low-density liquid, separated by a coexistence line that terminates in an LLCP. If the LLCP is real, it is located within No Man's Land (NML), the region of the metastable phase diagram that is difficult to access using conventional experimental techniques due to rapid homogeneous nucleation to the crystal. However, a recent ingenious experiment has enabled measurement of the diffusion constant deep inside NML. In the current communication, these recent measurements are compared, with good agreement, to the diffusion constant of E3B3 water, a classical water model that explicitly includes three-body interactions. The behavior of the diffusion constant as the system crosses the Widom line (the extension of the liquid-liquid coexistence line into the one-phase region) is analyzed to derive information about the presence and location of the LLCP. Calculations over a wide range of temperatures and pressures show that the new experimental measurements are consistent with an LLCP having a critical pressure of over 0.6 kbar.

Extended-Charge-Transfer Excitons in Crystalline Supramolecular Photocatalytic Scaffolds.

Coupling among chromophores in molecular assemblies is responsible for phenomena such as resonant energy transfer and intermolecular charge transfer. These processes are central to the fields of organic photovoltaics and photocatalysis, where it is necessary to funnel energy or charge to specific regions within the system. As such, a fundamental understanding of these transport processes is essential for developing new materials for photovoltaic and photocatalytic applications. Recently, photocatalytic systems based on photosensitizing perylene monomimide (PMI) chromophore amphiphiles were found to show variation in hydrogen gas (H2) production as a function of nanostructure crystallinity. The 2D crystalline systems form in aqueous electrolyte solution, which provides a high dielectric environment where the Coulomb potential between charges is mitigated. This results in relatively weakly bound excitons that are ideal for reducing protons. In order to understand how variations in crystalline structure affect H2 generation, two representative PMI systems are investigated theoretically using a modified Holstein Hamiltonian. The Hamiltonian includes both molecular Frenkel excitations (FE) and charge-transfer excitations (CTE) coupled nonadiabatically to local intramolecular vibrations. Signatures of FE/CTE mixing and the extent of electron/hole separation are identified in the optical absorption spectrum and are found to correlate strongly to the observed H2 production rates. The absorption spectral signatures are found to sensitively depend on the relative phase between the electron and hole transfer integrals, as well as the diabatic energy difference between the Frenkel and CT exciton bands. Our analysis provides design rules for artificial photosynthetic systems based on organic chromophore arrays.

Interference between Coulombic and CT-mediated couplings in molecular aggregates: H- to J-aggregate transformation in perylene-based π-stacks.

The spectroscopic differences between J and H-aggregates are traditionally attributed to the spatial dependence of the Coulombic coupling, as originally proposed by Kasha. However, in tightly packed molecular aggregates wave functions on neighboring molecules overlap, leading to an additional charge transfer (CT) mediated exciton coupling with a vastly different spatial dependence. The latter is governed by the nodal patterns of the molecular LUMOs and HOMOs from which the electron (te) and hole (th) transfer integrals derive. The sign of the CT-mediated coupling depends on the sign of the product teth and is therefore highly sensitive to small (sub-Angstrom) transverse displacements or slips. Given that Coulombic and CT-mediated couplings exist simultaneously in tightly packed molecular systems, the interference between the two must be considered when defining J and H-aggregates. Generally, such π-stacked aggregates do not abide by the traditional classification scheme of Kasha: for example, even when the Coulomb coupling is strong the presence of a similarly strong but destructively interfering CT-mediated coupling results in "null-aggregates" which spectroscopically resemble uncoupled molecules. Based on a Frenkel/CT Holstein Hamiltonian that takes into account both sources of electronic coupling as well as intramolecular vibrations, vibronic spectral signatures are developed for integrated Frenkel/CT systems in both the perturbative and resonance regimes. In the perturbative regime, the sign of the lowest exciton band curvature, which rigorously defines J and H-aggregation, is directly tracked by the ratio of the first two vibronic peak intensities. Even in the resonance regime, the vibronic ratio remains a useful tool to evaluate the J or H nature of the system. The theory developed is applied to the reversible H to J-aggregate transformations recently observed in several perylene bisimide systems.

The red-phase of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV): a disordered HJ-aggregate.

The ratio of the 0-0 to 0-1 peak intensities in the photoluminescence (PL) spectrum of red-phase poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], better known as MEH-PPV, is significantly enhanced relative to the disordered blue-phase and is practically temperature independent in the range from T = 5 K to 180 K. The PL lifetime is similarly temperature independent. The measured trends are accounted for by modeling red-phase MEH-PPV as disordered π-stacks of elongated chains. Using the HJ-aggregate Hamiltonian expanded to include site disorder amongst electrons and holes, the absorption and PL spectra of cofacial MEH-PPV dimers are calculated. The PL 0-0/0-1 line strength ratio directly responds to the competition between intrachain interactions which promote J-aggregate-like behavior (enhanced PL ratio) and interchain interactions which promote H-aggregate-like behavior (attenuated PL ratio). In MEH-PPV aggregates, J-like behavior is favored by a relatively large intrachain exciton bandwidth--roughly an order of magnitude greater than the interchain bandwidth--and the presence of disorder. The latter is essential for allowing 0-0 emission at low temperatures, which is otherwise symmetry forbidden. For Gaussian disorder distributions consistent with the measured (inhomogeneous) line widths of the vibronic peaks in the absorption spectrum, calculations show that the 0-0 peak maintains its dominance over the 0-1 peak, with the PL ratio and radiative lifetime practically independent of temperature, in excellent agreement with experiment. Interestingly, interchain interactions lead only to about a 30% drop in the PL ratio, suggesting that the MEH-PPV π-stacks--and strongly disordered HJ-aggregates in general--can masquerade as single (elongated) chains. Our results may have important applications to other emissive conjugated polymers such as the ß-phase of polyfluorenes.

OH-Stretch Raman Multivariate Curve Resolution Spectroscopy of HOD/H2O Mixtures.

Recently, in an attempt to quantify the role of intermolecular OH stretching vibrational couplings in liquid water, experimental Raman spectra of HOD/H2O mixtures were analyzed using the multivariate curve resolution (Raman-MCR) algorithm. This algorithm allowed for the separation of the HOD solute-correlated spectrum from the spectrum of bulk water. The former spectrum highlights features arising from HOD itself as well as from perturbations it induces on the surrounding H2O molecules. In this work, we apply a mixed quantum-classical methodology developed in our group to simulate the isotropic Raman-MCR spectra of HOD/H2O mixtures. Our results illustrate that intermolecular coupling leads to broadening and a red shift of the OH stretching band, in good agreement with the experiment. Our theoretical analysis provides a molecular-level interpretation of Raman-MCR experiments on HOD/H2O mixtures, suggesting that perturbations affecting the OH stretching vibrational mode of HOD result from intermolecular vibrational coupling to surrounding H2O molecules extending well beyond the first solvation shell.

Enhanced Davydov Splitting in Crystals of a Perylene Diimide Derivative.

We report the polarized absorption spectra of high-quality, thin crystals of a perylene diimide (PDI) species with branched side chains (B2). The absorption spectrum shows exemplary polarization-dependent H-like and J-like aggregate behavior upon orthogonal excitation, with a sizable Davydov splitting (DS) of 1230 cm-1 and peak to peak splitting of 3040 cm-1. The experimental results are compared to theoretical calculations with remarkable agreement. The theoretical analysis of the polarized absorption spectra shows evidence of a high degree of intermolecular charge transfer, which, along with Coulombic coupling, conspires to create the unprecedented DS for this family of dye molecules. The large polarization dependence of the electronic spectra is attributed to the unique twisted crystal structure, in which a substantial rotational displacement exists between neighboring chromophores within a π-stack. These results highlight the strong sensitivity of the Davydov splitting to intermolecular geometry in PDI systems.

The effect of chain bending on the photophysical properties of conjugated polymers.

The impact of chain bending on the photophysical properties of emissive conjugated polymers (CPs) is studied theoretically using Holstein-style Hamiltonians which treat vibronic coupling involving the ubiquitous vinyl/ring stretching mode nonadiabatically. The photophysical impact of chain bending is already evident at the level of an effective Frenkel Hamiltonian, where the positive exciton band curvature in CPs translates to negative excitonic coupling between monomeric units, as in J-aggregates. It is shown that the absorption and photoluminescence (PL) spectral line shapes respond very differently to chain bending. The misalignment of monomeric transition dipole moments with bending selectively attenuates the 0-0 PL peak intensity while leaving the 0-1 intensity practically unchanged, a property which is ultimately due to the uniquely coherent nature of the 0-0 peak. Hence, the 0-0/0-1 PL ratio, as well as the radiative decay rate, decrease with chain bending, effects that are more pronounced at lower temperatures where exciton coherence extends over a larger portion of the chain. Increasing temperature and/or static disorder reduces the exciton coherence number, Ncoh, thereby reducing the sensitivity to bending. In marked contrast, the absorption vibronic progression is far less sensitive to morphological changes, even at low temperatures, and is mainly responsive to the exciton bandwidth. The above results also hold when using a more accurate 1D semiconductor Hamiltonian which allows for electron-hole separation along the CP chain. The findings may suggest unique ways of controlling the radiative properties of conjugated polymer chains useful in applications such as organic light emitting diodes (OLEDs) and low-temperature sensors.