Depleted Oxygen Defect State Enhancing Tungsten Trioxide Photocatalysis: A Quantum Dynamics Perspective.

Oxygen vacancies generally create midgap states in transition metal oxides, which are expected to decrease the photoelectrochemical water-splitting efficiency. Recent experiments defy this expectation but leave the mechanism unclear. Focusing on the photoanode WO3 as a prototypical system, we demonstrate using nonadiabatic molecular dynamics that an oxygen vacancy suppresses nonradiative electron-hole recombination, because the defect acts as an electron reservoir instead of a recombination center. The occupied midgap electrons prefer to be populated a priori compared to the band edge transition because of a larger transition dipole moment, converting to depleted/unoccupied trap states that rapidly accept conduction band electrons and then cause trap-assisted recombination by impeding the bandgap recombination regardless of oxygen vacancy configurations. The reported results provide a fundamental understanding of the "realistic" role of the oxygen vacancies and their influence on charge-phonon dynamics and carrier lifetime. The study generates valuable insights into the design of high-performance transition metal oxide photocatalysts.

Photoinduced Energy Transfer in Linear Guest-Host Chromophores: A Computational Study.

Polymer-based guest-host systems represent a promising class of materials for efficient light-emitting diodes. The energy transfer from the polymer host to the guest is the key process in light generation. Therefore, microscopic descriptions of the different mechanisms involved in the energy transfer can contribute to enlighten the basis of the highly efficient light harvesting observed in this kind of materials. Herein, the nature of intramolecular energy transfer in a dye-end-capped conjugated polymer is explored by using atomistic nonadiabatic excited-state molecular dynamics. Linear perylene end-capped (PEC) polyindenofluorenes (PIF), consisting of n (n = 2, 4, and 6) repeat units, i.e., PEC-PIFn oligomers, are considered as model systems. After photoexcitation at the oligomer absorption maximum, an initial exciton becomes self-trapped on one of the monomer units (donors). Thereafter, an efficient ultrafast through-space energy transfer from this unit to the perylene acceptor takes place. We observe that this energy transfer occurs equally well from any monomer unit on the chain. Effective specific vibronic couplings between each monomer and the acceptor are identified. These oligomer → end-cap energy transfer steps do not match with the rates predicted by Förster-type energy transfer. The through-space and through-bond mechanisms are two distinct channels of energy transfer. The former dominates the overall process, whereas the through-bond energy transfer between indenofluorene monomer units along the oligomer backbone only makes a minor contribution.

Controlling Charge Carrier Trapping and Recombination in BiVO4 with the Oxygen Vacancy Oxidation State.

The lack of an in-depth understanding of the intrinsic oxygen vacancy (OV) defect properties in the photoanode BiVO4 limits the further improvement of its photoelectrochemical water splitting performance. To address this issue, nonadiabatic molecular dynamics simulations are performed to study the impact of OV on charge carrier lifetimes in BiVO4. The simulations show that a neutral OV gives rise to local structural distortions due to the formation of V-O-V bonds, forcing the electrons trapped on the nearer of the two V atoms to form two deep polaron-like V4+ hole traps. These localized midgap states greatly accelerate nonradiative electron-hole recombination compared to that of pristine BiVO4, reaching a time scale of several nanoseconds in good agreement with experiments. The ionized OV state restores the bandgap to its value in pristine BiVO4 and restores the charge carrier lifetimes due to the fast loss of coherence time. Our study reveals the mechanism of the detrimental role of OV in BiVO4 and provides valuable insights for improving the performance of the BiVO4 photoanode by ionizing the oxygen vacancy.

Photoinduced Dynamics with Constrained Vibrational Motion: FrozeNM Algorithm.

Ab initio molecular dynamics (AIMD) simulation, analyzed in terms of vibrational normal modes, is a widely used technique that facilitates understanding of complex structural motions and coupling between electronic and nuclear degrees of freedom. Usually, only a subset of vibrations is directly involved in the process of interest. The impact of these vibrations can be evaluated by performing AIMD simulations by selectively freezing certain motions. Herein, we present frozen normal mode (FrozeNM), a new algorithm to apply normal-mode constraints in AIMD simulations, as implemented in the nonadiabatic excited state molecular dynamics code. We further illustrate its capacity by analyzing the impact of normal-mode constraints on the photoinduced energy transfer between polyphenylene ethynylene dendrimer building blocks. Our results show that the electronic relaxation can be significantly slowed down by freezing a well-selected small subset of active normal modes characterized by their contributions in the direction of energy transfer. The application of these constraints reduces the nonadiabatic coupling between electronic excited states during the entire dynamical simulations. Furthermore, we validate reduced dimensionality models by freezing all the vibrations, except a few active modes. Altogether, we consider FrozeNM as a useful tool that can be broadly used to underpin the role of vibrational motion in a studied process and to formulate reduced models that describe essential physical phenomena.

Vibrational energy redistribution during donor-acceptor electronic energy transfer: criteria to identify subsets of active normal modes.

Photoinduced electronic energy transfer in conjugated donor-acceptor systems is naturally accompanied by intramolecular vibrational energy redistributions accepting an excess of electronic energy. Herein, we simulate these processes in a covalently linked donor-acceptor molecular dyad system by using nonadiabatic excited state molecular dynamics simulations. We analyze different complementary criteria to systematically identify the subset of vibrational normal modes that actively participate on the donor → acceptor (S2→ S1) electronic relaxation. We analyze energy transfer coordinates in terms of state-specific normal modes defined according to the different potential energy surfaces (PESs) involved. On one hand, we identify those vibrations that contribute the most to the direction of the main driving force on the nuclei during electronic transitions, represented by the non-adiabatic derivative coupling vector between donor and acceptor electronic states. On the other hand, we monitor normal mode transient accumulations of excess energy and their intramolecular energy redistribution fluxes. We observe that the subset of active modes varies according to the PES on which they belong and these modes experience the most significant rearrangements and mixing. Whereas the nuclear motions that promote donor → acceptor energy funneling can be localized mainly on one or two normal modes of the S2 state, they become spread out across multiple normal modes of the S1 state following the energy transfer event.

Photoexcited energy relaxation and vibronic couplings in π-conjugated carbon nanorings.

Conjugated carbon nanorings exhibit unique photophysical properties that, combined with their tunable sizes and conformations, make them suitable for a variety of practical applications. These properties are intimately associated to their strained, bent and sterically hindered cyclic structures. Herein we perform a comparative analysis of the photoinduced dynamics in carbon nanorings composed of nine phenyl units([9]CPP) and nine naphthyl units ([9]CN) respectively. The sterically demanding naphthyl units lead to large dihedral angles between neighboring units. Nevertheless, the ultrafast electronic and vibrational energy relaxation and redistribution is found to be similar for both systems. We observe that vibronic couplings, introduced by nonadiabatic energy transfer between electronic excited states, ensure the intramolecular vibrational energy redistribution through specific vibrational modes. The comparative impact of the internal conversion process on the exciton spatial localization and intra-ring migration indicates that naphthyl units in [9]CN achieve more efficient but less dynamical self-trapping compared to that of phenyl units in [9]CPP. That is, during the photoinduced process, the exciton in [9]CN is more static and localized than the exciton in [9]CPP. The internal conversion processes take place through a specific set of middle- to high-frequency normal modes, which directly influence the spatial exciton redistribution during the internal conversion, self-trapping and intra-ring migration.

Electronic Energy Relaxation in a Photoexcited Fully Fused Edge-Sharing Carbon Nanobelt.

Carbon nanobelts are cylindrical molecules composed of fully fused edge-sharing arene rings. Because of their aesthetically appealing structures, they acquire unusual optoelectronic properties that are potentially suitable for a range of applications in nanoelectronics and photonics. Nevertheless, the very limited success of their synthesis has led to their photophysical properties remaining largely unknown. Compared to that of carbon nanorings (arenes linked by single bonds), the strong structural rigidity of nanobelts prevents significant deformations away from the original high-symmetry conformation and, therefore, impacts their photophysical properties. Herein, we study the photoinduced dynamics of a successfully synthesized belt segment of (6,6)CNT (carbon nanotube). Modeling this process with nonadiabatic excited state molecular dynamics simulations uncovers the critical role played by the changes in excited state wave function localization on the different types of carbon atoms. This allows a detailed description of the excited state dynamics and spatial exciton evolution throughout the nanobelt scaffold. Our results provide detailed information about the excited state electronic properties and internal conversion rates that is potentially useful for designing nanobelts for nanoelectronic and photonic applications.

Vibronic Quantum Beating between Electronic Excited States in a Heterodimer.

Energy transfer in multichromophoric molecules can be affected by coherences that are induced by the electronic and vibrational couplings between chromophore units. Coherent electron-vibrational dynamics can persist at the subpicosecond time scale even at room temperature. Furthermore, wave-like localized-delocalized motions of the electronic wave function can be modulated by vibrations that actively participate in the intermolecular energy transfer process. Herein, nonadiabatic excited state molecular dynamics simulations have been performed on a rigid synthetic heterodimer that has been proposed as a simplified model for investigating the role and mechanism of coherent energy transfer in multichromophoric systems. Both surface hopping (SH) and Ehrenfest approaches (EHR) have been considered. After photoexcitation of the system at room temperature, EHR simulations reveal an ultrafast beating of electronic populations between the two lowest electronic states. These oscillations are not observed at low temperature and have vibrational origins. Furthermore, they cannot be reproduced using SH approach. This periodic behavior of electronic populations induces oscillations in the spatial localization of the electronic transition density between monomers. Vibrations whose frequencies are near-resonant with energy difference between the two lowest electronic excited states are in the range of the electronic population beating, and they are the ones that contribute the most to the coherent dynamics of these electronic transitions.

Fatty Acid and Retinol-Binding Protein: Unusual Protein Conformational and Cavity Changes Dictated by Ligand Fluctuations.

Lipid-binding proteins (LBPs) are soluble proteins responsible for the uptake, transport, and storage of a large variety of hydrophobic lipophilic molecules including fatty acids, steroids, and other lipids in the cellular environment. Among the LBPs, fatty acid binding proteins (FABPs) present preferential binding affinities for long-chain fatty acids. While most of FABPs in vertebrates and invertebrates present similar ß-barrel structures with ligands accommodated in their central cavity, parasitic nematode worms exhibit additional unusual α-helix rich fatty acid- and retinol-binding proteins (FAR). Herein, we report the comparison of extended molecular dynamics (MD) simulations performed on the ligand-free and palmitic acid-bond states of the Necator americanus FAR-1 (Na-FAR-1) with respect to other classical ß-barrel FABPs. Principal component analysis (PCA) has been used to identify the different conformations adopted by each system during MD simulations. The α-helix fold encompasses a complex internal ligand-binding cavity with a remarkable conformational plasticity that allows reversible switching between distinct states in the holo-Na-FAR-1. The cavity can change up to one-third of its size affected by conformational changes of the protein-ligand complex. Besides, the ligand inside the cavity is not fixed but experiences large conformational changes between bent and stretched conformations. These changes in the ligand conformation follow changes in the cavity size dictated by the transient protein conformation. On the contrary, protein-ligand complex in ß-barrel FABPs fluctuates around a unique conformation. The significantly more flexible holo-Na-FAR-1 ligand-cavity explains its larger ligand multiplicity respect to ß-barrel FABPs.

Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks.

The efficiency of the intramolecular energy transfer in light harvesting dendrimers is determined by their well-defined architecture with high degree of order. After photoexcitation, through-space and through-bond energy transfer mechanisms can take place, involving vectorial exciton migration among different chromophores within dendrimer highly branched structures. Their inherent intramolecular energy gradient depends on how the multiple chromophoric units have been assembled, subject to their inter-connects, spatial distances, and orientations. Herein, we compare the photoinduced nonadiabatic molecular dynamics simulations performed on a set of different combinations of a chain of linked dendrimer building blocks composed of two-, three-, and four-ring linear polyphenylene chromophoric units. The calculations are performed with the recently developed ab initio multiple cloning-time dependent diabatic basis implementation of the Multiconfigurational Ehrenfest (MCE) approach. Despite differences in short time relaxation pathways and different initial exciton localization, at longer time scales, electronic relaxation rates and exciton final redistributions are very similar for all combinations. Unlike the systems composed of two building blocks, considered previously, for the larger 3 block systems here we observe that bifurcation of the wave function accounted by cloning is important. In all the systems considered in this work, at the time scale of few hundreds of femtoseconds, cloning enhances the electronic energy relaxation by ∼13% compared to that of the MCE method without cloning. Thus, accurate description of quantum effects is essential for understanding of the energy exchange in dendrimers both at short and long time scales.

Energy transfer and spatial scrambling of an exciton in a conjugated dendrimer.

Photoexcitation of multichromophoric light harvesting molecules induces a number of intramolecular electronic energy relaxation and redistribution pathways that can ultimately lead to ultrafast exciton self-trapping on a single chromophore unit. We investigate the photoinduced processes that take place on a phenylene-ethynylene dendrimer, consisting of nine equivalent linear chromophore units or branches. meta-Substituted links between branches break the conjugation giving rise to weak couplings between them and to localized excitations. Our nonadiabatic excited-state molecular dynamics simulations reveal that the ultrafast internal conversion process to the lowest excited state is accompanied by an inner → outer inter-branch migration of the exciton due to the entropic bias associated with energetically equivalent conjugated segments. The electronic energy redistribution among chromophore units occurs through several possible pathways in which through-bond transport and through-space exciton hopping mechanisms can be distinguished. Besides, triple bond excitations coincide with the localization of the electronic transition densities, suggesting that the intramolecular energy redistribution is a concerted electronic and vibrational energy transfer process.

Photoinduced dynamics in cycloparaphenylenes: planarization, electron-phonon coupling, localization and intra-ring migration of the electronic excitation.

Cycloparaphenylenes represent the smallest possible fragments of armchair carbon nanotubes. Due to their cyclic and curved conjugation, these nanohoops own unique photophysical properties. Herein, the internal conversion processes of cycloparaphenylenes of sizes 9 through 16 are simulated using Non-Adiabatic Excited States Molecular Dynamics. In order to analyze effects of increased conformational disorder, simulations are done at both low temperature (10 K) and room temperature (300 K). We found the photoexcitation and subsequent electronic energy relaxation and redistribution lead to different structural and electronic signatures such as planarization of the chain, electron-phonon couplings, wavefunction localization, and intra-ring migration of excitons. During excited state dynamics on a picosecond time-scale, an electronic excitation becomes partially localized on a portion of the ring (about 3-5 phenyl rings), which is not a mere static contraction of the wavefunction. In a process of non-radiative relaxation involving non-adiabatic transitions, the latter exhibits significant dynamical mobility by sampling uniformly the entire molecular structure. Such randomized migration involving all phenyl rings, occurs in a wave-like fashion coupled to vibrational degrees of freedom. These results can be connected to unpolarized emission observed in single-molecule fluorescence experiments. Observed intra-ring energy transfer is subdued for lower temperatures and adiabatic dynamics involving low-energy photoexcitation to the first excited state. Overall our analysis provides a detailed description of photo excited dynamics in molecular systems with circular geometry, outlines size-dependent trends and connotes specific spectroscopic signatures appearing in time-resolved experimental probes.

Ultrafast electronic energy relaxation in a conjugated dendrimer leading to inter-branch energy redistribution.

Dendrimers are arrays of coupled chromophores, where the energy of each unit depends on its structure and conformation. The light harvesting and energy funneling properties are strongly dependent on their highly branched conjugated architecture. Herein, the photoexcitation and subsequent ultrafast electronic energy relaxation and redistribution of a first generation dendrimer (1) are analyzed combining theoretical and experimental studies. Dendrimer 1 consists of three linear phenylene-ethynylene (PE) units, or branches, attached in the meta position to a central group opening up the possibility of inter-branch energy transfer. Excited state dynamics are explored using both time-resolved spectroscopy and non-adiabatic excited state molecular dynamics simulations. Our results indicate a subpicosecond loss of anisotropy due to an initial excitation into several states with different spatial localizations, followed by exciton self-trapping on different units. This exciton hops between branches. The absence of an energy gradient leads to an ultrafast energy redistribution among isoenergetic chromophore units. At long times we observe similar probabilities for each branch to retain significant contributions of the transition density of the lowest electronic excited-state. The observed unpolarized emission is attributed to the contraction of the electronic wavefunction onto a single branch with frequent interbranch hops, and not to its delocalization over the whole dendrimer.

Carbon nanorings with inserted acenes: breaking symmetry in excited state dynamics.

Conjugated cycloparaphenylene rings have unique electronic properties being the smallest segments of carbon nanotubes. Their conjugated backbones support delocalized electronic excitations, which dynamics is strongly influenced by cyclic geometry. Here we present a comparative theoretical study of the electronic and vibrational energy relaxation and redistribution in photoexcited cycloparaphenylene carbon nanorings with inserted naphthalene, anthracene, and tetracene units using non-adiabatic excited-state molecular dynamics simulations. Calculated excited state structures reflect modifications of optical selection rules and appearance of low-energy electronic states localized on the acenes due to gradual departure from a perfect circular symmetry. After photoexcitation, an ultrafast electronic energy relaxation to the lowest excited state is observed on the time scale of hundreds of femtoseconds in all molecules studied. Concomitantly, the efficiency of the exciton trapping in the acene raises when moving from naphthalene to anthracene and to tetracene, being negligible in naphthalene, and ~60% and 70% in anthracene and tetracene within the first 500 fs after photoexcitation. Observed photoinduced dynamics is further analyzed in details using induced molecular distortions, delocatization properties of participating electronic states and non-adiabatic coupling strengths. Our results provide a number of insights into design of cyclic molecular systems for electronic and light-harvesting applications.

Computational study of photoexcited dynamics in bichromophoric cross-shaped oligofluorene.

The non-adiabatic excited state molecular dynamics (NA-ESMD) approach is applied to investigate photoexcited dynamics and relaxation pathways in a spiro-linked conjugated polyfluorene at room (T = 300 K) and low (T = 10 K) temperatures. This dimeric aggregate consists of two perpendicularly oriented weakly interacting α-polyfluorene oligomers. The negligible coupling between the monomer chains results in an initial absorption band composed of equal contributions of the two lowest excited electronic states, each localized on one of the two chains. After photoexcitation, an efficient ultrafast localization of the entire electronic population to the lowest excited state is observed on the time scale of about 100 fs. Both internal conversion between excited electronic states and vibronic energy relaxation on a single electronic state contribute to this process. Thus, photoexcited dynamics of the polyfluorene dimer follows two distinct pathways with substantial temperature dependence on their efficiency. One relaxation channel involves resonance electronic energy transfer between the monomer chains, whereas the second pathway concerns the relaxation of the electronic energy on the same chain that has been initially excited due to electron-phonon coupling. Despite the slower vibrational relaxation, a more efficient ultrafast electronic relaxation is observed at low temperature. Our numerical simulations analyze the effects of molecular geometry distortion during the electronic energy redistribution and suggest spectroscopic signatures reflecting complex electron-vibrational dynamics.

Shishiodoshi unidirectional energy transfer mechanism in phenylene ethynylene dendrimers.

Non-adiabatic excited-state molecular dynamics is used to study the ultrafast intramolecular energy transfer between two-, three-, and four-ring linear polyphenylene ethynylene chromophore units linked through meta-substitutions. Twenty excited-state electronic energies, with their corresponding gradients and nonadiabatic coupling vectors were included in the simulations. The initial laser excitation creates an exciton delocalized between the different absorbing two-ring linear PPE units. Thereafter, we observe an ultrafast directional change in the spatial localization of the transient electronic transition density. The analysis of the intramolecular flux of the transition density shows a sequential through-bond two-ring→three-ring→four-ring transfer as well as an effective through-space direct two-to-four ring transfer. The vibrational excitations of C≡C stretching motions change according to that. Finally, a mechanism of unidirectional energy transfer is presented based on the variation of the energy gaps between consecutive electronic excited states in response to the intramolecular flux of the transition density. The mechanism resembles a Shishiodoshi Japanese bamboo water fountain where, once the electronic population has been transferred to the state directly below in energy, the two states decouple thereby preventing energy transfer in the opposite direction.

Sulfide-binding hemoglobins: Effects of mutations on active-site flexibility.

The dynamics of Hemoglobin I (HbI) from the clam Lucina pectinata, from wild-type sperm whale (SW) myoglobin, and from the L29F/H64Q/V68F triple mutant of SW, both unligated and bound to hydrogen sulfide (H2S), have been studied in molecular dynamics simulations. Features that account for differences in H2S affinity among the three have been examined. Our results verify the existence of an unusual heme rocking motion in unligated HbI that can promote the entrance of large ligands such as H2S. The FQF-mutant partially reproduces the amplitude and relative orientation of the motion of HbI's heme group. Therefore, besides introducing favorable electrostatic interactions with H2S, the three mutations in the distal pocket change the dynamic properties of the heme group. The active-site residues Gln-64(E7), Phe-43(CD1), and His-93(F8) are also shown to be more flexible in unligated HbI than in FQF-mutant and SW. Further contributions to H2S affinity come from differences in hydrogen bonding between the heme propionate groups and nearby amino acid residues.