Electron-vibration Coupling Research Articles

Development of Two-Dimensional Electronic-Vibrational Sum Frequency Generation (2D-EVSFG) for Vibronic and Solvent Couplings of Molecules at Interfaces and Surfaces.

Many photoinduced excited states' relaxation processes and chemical reactions occur at interfaces and surfaces, including charge transfer, energy transfer, proton transfer, proton-coupled electron transfer, configurational dynamics, conical intersections, etc. Of them, interactions of electronic and vibrational motions, namely, vibronic couplings, are the main determining factors for the relaxation processes or reaction pathways. However, time-resolved electronic-vibrational spectroscopy for interfaces and surfaces is lacking. Here we develop interface/surface-specific two-dimensional electronic-vibrational sum frequency generation spectroscopy (2D-EVSFG) for time-dependent vibronic coupling of excited states at interfaces and surfaces. We further demonstrate the fourth-order technique by investigating vibronic coupling, solvent correlation, and time evolution of the coupling for photoexcited interface-active molecules, crystal violet (CV), at the air/water interface as an example. The two vibronic absorption peaks for CV molecules at the interface from the 2D-EVSFG experiments were found to be more prominent than their counterparts in bulk from 2D-EV. Quantitative analysis of the vibronic peaks in 2D-EVSFG suggested that a non-Condon process participates in the photoexcitation of CV at the interface. We further reveal vibrational solvent coupling for the zeroth level on the electronic state with respect to that on the ground state, which is directly related to the magnitude of its change in solvent reorganization energy. The change in the solvent reorganization energy at the interface is much smaller than that in bulk methanol. Time-dependent center line slopes (CLSs) of 2D-EVSFG also showed that kinetic behaviors of CV at the air/water interface are significantly different from those in bulk methanol. Our ultrafast 2D-EVSFG experiments not only offer vibrational information on both excited states and the ground state as compared with the traditional doubly resonant sum frequency generation and electronic-vibrational coupling but also provide vibronic coupling, dynamical solvent effects, and time evolution of vibronic coupling at interfaces.

Frontispiece: Molecular Design of A−D−A Electron Acceptors Towards Low Energy Loss for Organic Solar Cells

To achieve high photovoltaic efficiency in organic solar cells, low energy loss is especially important. Electron-vibration coupling plays a significant role in reducing the energy loss. Read more about recent theoretical advances on revealing the energy loss mechanisms at the molecular level in the Concept article by L. Zhu, Y. Yi et al. (DOI: 10.1002/chem.202203356).

Dynamics of an excitation-transfer trimer: Interference, coherence, Berry's phase development, and vibrational control of non-adiabaticity.

We detail several interesting features in the dynamics of an equilaterally shaped electronic excitation-transfer (EET) trimer with distance-dependent intermonomer excitation-transfer couplings. In the absence of electronic-vibrational coupling, symmetric and antisymmetric superpositions of two single-monomer excitations are shown to exhibit purely constructive, oscillatory, and purely destructive interference in the EET to the third monomer, respectively. In the former case, the transfer is modulated by motion in the symmetrical framework-expansion vibration induced by the Franck-Condon excitation. Distortions in the shape of the triangular framework degrade that coherent EET while activating excitation transfer in the latter case of an antisymmetric initial state. In its symmetrical configuration, two of the three single-exciton states of the trimer are degenerate. This degeneracy is broken by the Jahn-Teller-active framework distortions. The calculations illustrate closed, approximately circular pseudo-rotational wave-packet dynamics on both the lower and the upper adiabatic potential energy surfaces of the degenerate manifold, which lead to the acquisition after one cycle of physically meaningful geometric (Berry) phases of π. Another manifestation of Berry-phase development is seen in the evolution of the vibrational probability density of a wave packet on the lower Jahn-Teller adiabatic potential comprising a superposition of clockwise and counterclockwise circular motions. The circular pseudo-rotation on the upper cone is shown to stabilize the adiabatic electronic state against non-adiabatic internal conversion via the conical intersection, a dynamical process analogous to Slonczewski resonance. Strategies for initiating and monitoring these various dynamical processes experimentally using pre-resonant impulsive Raman excitation, short-pulse absorption, and multi-dimensional wave-packet interferometry are outlined in brief.

Inelastic squared form factors of the vibronic states of B1Σu+, C1Πu , and EF1Σg+ for molecular D2 studied by high-energy electron scattering

The inelastic squared form factors of the valence-shell excitations of ${\mathrm{D}}_{2}$ were measured by high-energy electron scattering and calculated by the multireference single- and double-excitation configuration interaction method in the present work. It is found that for the ${B}^{1}{\mathrm{\ensuremath{\Sigma}}}_{u}{}^{+}$ state of ${\mathrm{D}}_{2}$, the theoretical calculation cannot satisfactorily reproduce the inelastic squared form factors with a higher vibrational quantum number. For the vibronic states of ${C}^{1}{\mathrm{\ensuremath{\Pi}}}_{u}$ and $E{F}^{1}{\mathrm{\ensuremath{\Sigma}}}_{g}{}^{+}$ of ${\mathrm{D}}_{2}$, obvious discrepancies between our electron-scattering results and theoretical calculations are found. Similar phenomena observed for ${\mathrm{H}}_{2}$, HD, and ${\mathrm{D}}_{2}$ may be attributed to electronic-vibrational coupling and the failure of the first Born approximation at an incident electron energy of 1500 eV. Furthermore, the present inelastic squared form factors of ${\mathrm{D}}_{2}$ are in good agreement with the ones of ${\mathrm{H}}_{2}$ and HD, which indicates that there is no isotope effect for the electronic matrix elements of ${\mathrm{H}}_{2}$, HD, and ${\mathrm{D}}_{2}$ in the momentum space.

Molecular Design of A-D-A Electron Acceptors Towards Low Energy Loss for Organic Solar Cells.

Low energy loss is a prerequisite for organic solar cells to achieve high photovoltaic efficiency. Electron-vibration coupling (i. e., intramolecular reorganization energy) plays a crucial role in the photoelectrical conversion and energy loss processes. In this Concept article, we summarize our recent theoretical advances on revealing the energy loss mechanisms at the molecular level of A-D-A electron acceptors. We underline the importance of electron-vibration couplings on reducing the energy loss and describe the effective molecular design strategies towards low energy loss through decreasing the electron-vibration couplings.

Passivation of Hematite by a Semiconducting Overlayer Reduces Charge Recombination: An Insight from Nonadiabatic Molecular Dynamics.

Hematite (α-Fe2O3) is a promising photoanode material for photoelectrochemical water splitting. Surface-passivating layers are effective in improving water oxidation kinetics; however, the passivation mechanism is not fully understood due to the complexity of interfacial reactions. Focusing on the Fe-terminated Fe2O3 (0001) surface that exhibits surface states in the band gap, we perform ab initio quantum dynamics simulations to study the effect of an α-Ga2O3 overlayer on charge recombination. The overlayer eliminates surface states and suppresses charge recombination 4-fold. This explains in part the observed cathodic shift in the onset potential for water oxidation. The increased charge carrier lifetime is an outcome of two factors, energy gap and electron-vibrational coupling, with a positive contribution from the former but a negative contribution from the latter. This work presents an advance in the atomistic time-domain understanding of the influence of surface passivation on charge recombination dynamics and provides guidance for designing novel α-Fe2O3 photoanodes.

Effect of bromine substitution on blue phosphorescent trans-(N-heterocyclic carbene)Pt(II) acetylide complexes.

N-heterocyclic carbene complexes of the type trans-(NHC)2PtII(CC-Ar)2 (where Ar = phenyl or substituted phenyl) are of interest as violet and blue phosphors. These complexes emit efficient phosphorescence in solution and in the solid state, and they have been applied as phosphors in organic light emitting diodes. This study explores the effect of bromine substitution on the trans-(NHC)2PtII(CC-Ar)2 chromophore through photophysical studies of a pair of complexes in which the phenyl groups feature either 3,5-dibromo- or 4-monobromo-substituents (IPt-DB and IPt-MB, respectively). The Br atoms were introduced as heavy atom(s) with the aim to enhance spin-orbit coupling and increase the radiative and non-radiative decay rates of the phosphorescent triplet state. Both IPt-MB and IPt-DB exhibit sky-blue phosphorescence in solution and in PMMA matrix. Interestingly, the emission quantum yield and lifetime of IPt-MB are substantially lower compared to IPt-DB in solution. This effect is attributed to a substantially larger non-radiative decay rate in the mono-bromo complex. Analysis of the photophysical data, combined with DFT and TD-DFT calculations, suggest that the difference in photophysical properties of the two complexes is related to the position of the Br-substituents on the phenyl acetylide rings. In short, in IPt-MB, the Br-substituents are located para-to the Pt-CC-unit, and this gives rise to stronger electron-vibrational coupling in the excited state, enhancing the rate of non-radiative decay.

Elucidation of the key role of isomerization in the self-assembly and luminescence properties of AIEgens.

Due to the hierarchical nature of the self-assembly process, it is effective to control assembled nanostructures by tuning the spatial configurations of the building blocks through Z-/E-isomerization. A pair of AIE stereoisomers termed (Z)-/(E)-TPE-UPy was reported with different self-assembly mechanisms, morphologies and luminescence properties. In this study, we present a multiscale modeling combining MD simulations, hybrid QM/MM calculations and the PCM model, to systematically clarify the molecular configuration-molecular assembly-photophysical property relationship of (Z)-/(E)-TPE-UPy. Our study shows that (Z)-TPE-UPy follows a concentration-dependent ring-chain polymerization mechanism. At low concentration, (Z)-TPE-UPy tends to form ring-like (Z)-close-dimers with all H-bond sites occupied, while at high concentration, the H-bond backbone in the chain-like structures is more planar and stronger, making the zig-zag chain-like conformations more favorable. For the (E)-isomer, the H-bond backbone is quite planar and rigid, which makes it linearly elongate one-by-one at the whole range of concentrations via the isodesmic polymerization mechanism. (Z)-TPE-UPy oligomers exhibit large flexibility and diverse conformations, leading to sharply enhanced viscosity at high concentration in experiments. Moreover, the fluorescence spectrum of (Z)-/(E)-TPE-UPy aggregate is conformation-dependent and the enhanced emission in the aggregated state is attributed to the restriction of the low-frequency intramolecular rotations of the phenyl rings and the distortion of the CC plane, as well as the reduction of electron-vibration couplings. Our work not only offers valuable insights into the key role of stereoisomerism in assembled morphologies and luminescence properties, but also provides a theoretical basis for the rational design of new building blocks based on stereoisomers.

Cr3+doped Ca3(VO4)2: A new tunable laser crystal

A new near-infrared tunable laser crystal, Cr3+ doped Ca3(VO4)2 crystal (Cr: CVO) is grown by the Czochralski method for the first time. The crystal structure and thermal expansion of Cr: CVO crystal are investigated in detail. The substitution of Cr3+ for Ca2+ is confirmed by the formation energy calculation. The Cr: CVO crystal has a strong and broad absorption at visible wavelength and a broad emission in the near-infrared. The absorption cross-section in the σ direction is about 1.56 times that in the π direction at 690 nm. A broadband emission extends from 750 nm to 1200 nm with the full width at half maximum 185 nm and 178 nm in the σ and π direction, respectively. The crystal field and electron-vibration coupling are discussed, as well as the origin of the broadband emission. While Cr3+ ions substitute other ions with a large difference in ionic radii and charges such as Ca2+ ions, the lattice distortion and vacancy may be produced, leading to the severe distortion of the octahedron and the broadening of the emission band. Our work guides the design of broadband luminescent materials and confirms that Cr: CVO is a potential candidate for tunable laser crystals.

Theoretical study on the vibrational structures in the conductance spectra of a weakly coupled polycyclic aromatic hydrocarbon molecule

The conductance spectra of a 5,10,15,20-tetraphenylbisbenz[5,6]indeno[1,2,3-cd: 1′,2′,3′-lm]perylene molecule that was experimentally studied recently were simulated based on density functional theory and Franck-Condon simulations. The vibrational structures in available experimental conductance spectra associated with different frontier orbitals of the molecule were nicely reproduced. The good agreement between simulated and experimental results enables the unambiguous identification of the vibrational modes involved in the charge transport processes. Differences to the vibrational progressions in the conductance spectra associated with the frontier orbitals were found to be caused by changes of the electron-vibration coupling properties of the corresponding electronic transitions.

Anion Doping Delays Nonradiative Electron-Hole Recombination in Cs-Based All-Inorganic Perovskites: Time Domain ab Initio Analysis.

Using time-domain density functional theory combined with nonadiabatic (NA) molecular dynamics, we demonstrate that composition engineering of the X-site anions has a strong influence on the nonradiative electron-hole recombination and thermodynamic stability of cesium-based all-inorganic perovskites. Partial substitution of iodine(I) with bromine (Br) and acetate (Ac) anions reduces the NA electron-vibrational coupling by minimizing the overlap between the electron and hole wave functions and suppressing atomic fluctuations. The doping also widens the energy gap to further reduce the NA coupling and to enhance the open-circuit voltage of perovskite solar cells. These factors increase the charge carrier lifetime by an order of magnitude and improve structural stability in the series CsPbI1.88BrAc0.12 > CsPbI2Br > CsPbI3. The fundamental atomistic insights into the influence of anion doping on the photophysical properties of the all-inorganic lead halide perovskites guide the design of efficient optoelectronic materials.

Problems of Quantum-Classical Modeling Of the Primary Photoreaction in Rhodopsin

A modified model of the primary photoreaction in rhodopsin, cis-trans photoisomerization of the chromophore (retinal), is studied. The quantum subsystem of the model includes three vibronic states: the ground state, the excited state, and the ground state of the primary photoproduct. These states correspond to three point masses in the classical subsystem. The modification consists in the exponential dependence of the electronic-vibrational coupling constant on the displacement of point masses. The properties of the optimal loci of the multiparameter space, which characterized by the best agreement with the experimental data, are studied. A rather small “multidimensional volume” of these loci shown in all ranges of the used values of the model parameters. Several ways to optimize the quantum-classical model of rhodopsin photoisomerization have been proposed.

Model for the dynamics of carrier injection in a band with polaronic states: Application to exciton dissociation in organic solar cells

We develop a quantum model for the dynamics of carrier injection in a band that presents a strong carrier-vibration coupling. This coupling modifies the spectral density of the band and can even create pseudogaps that signal the onset of polaronic states. The injection of a carrier that interacts with many vibration modes is a complex many-body process that is treated by combining the quantum scattering theory and the dynamical mean-field theory (DMFT). For the model analyzed here, which is adapted to compact phases, the number $Z$ of neighbors of a given site is large and in this limit the DMFT becomes exact. The model is applied to the excitonic dissociation at the donor-acceptor interface for organic solar cells. The main ingredients are the electron-hole Coulomb interaction, the recombination process, and the existence of polaronic states in the acceptor band. Using parameters extracted from ab initio calculations we analyze the spectral density on the charge transfer state (CTS), the average energy transferred to phonons on the CTS, and the quantum yield of the injection process. We find in particular that even with a strong electron-vibration coupling, one can get a vibrationally cold charge transfer state with a high injection yield as often observed experimentally.

Optimal Dihedral Angle in Twisted Donor-Acceptor Organic Emitters for Maximized Thermally Activated Delayed Fluorescence.

The twisted donor-acceptor (D-A) organic formwork with a large dihedral angle (θDA ) is usually adopted to narrow the singlet-triplet energy gap for obtaining excellent thermally activated delayed fluorescence (TADF) emitters. However, the dependence of overall TADF properties on θDA has not been systematically investigated to this day. Taking new designed CzBP, CzBP-1M and CzBP-2M via introducing methyl as investigated models, it is found that (i) with increasing θDA , the charge transfer component in S1 is larger than that in T1 in varying degrees, leading to non-monotonic spin-orbit couplings; (ii) the electron-vibration couplings between S1 and T1 states become the largest when θDA approaching 80°, facilitating phonon-driven up-conversion; (iii) the overall TADF rate reaches a peak at θDA ≈80°. By this, the TADF on/off switching is realized via methyl moiety for regulating θDA from theoretical prediction to experimental confirmation. Importantly, the θDA near 80° would be a good descriptor for screening excellent D-A type TADF emitters.

Bond-specific fragmentation of oligopeptides via electronic stopping of swift heavy ions in molecular films

Highly bond-specific fragmentation of oligopeptides induced by swift heavy ion (SHI) irradiation was investigated by means of mass spectrometry. In pronounced contrast to measurements of samples irradiated with keV ions, oligopeptides which were exposed to 946 MeV Au ions show a high abundance of specific fragments. The highly bond-specific nature of SHI-induced fragmentation is attributed to electronic stopping as the most relevant energy loss mechanism for SHI in the oligopeptide samples in combination with the subsequent coupling between the excited electronic and the atomic subsystem. Fragmentation induced by SHI is observed to be further influenced by the structure of the oligopeptides, suggesting that electronic excitation and/or the electronic-vibrational coupling depend on the details of the molecular structure.

Acceleration of Nonradiative Charge Recombination Reactions at Larger Distances in Kinked Donor-Bridge-Acceptor Molecules.

Photoinduced electron transfer in donor-bridge-acceptor (D-B-A) molecular systems can occur via tunneling over long distances (rDA) of well over 10 Å. We commonly observe decreasing rates of electron transfer with increasing distances, a result of a decrease in the electronic coupling of the donor and acceptor moiety. In the study of D-B-A molecules with Ru(bpy)32+ as a bridge/core, Kuss-Petermann and Wenger observed the opposite trend (J. Am. Chem. Soc.2016, 138, 1349); a maximum rate constant of electron transfer was observed at an intermediate electron transfer distance. Within the high-temperature limit of the classical Marcus equation, their observation was qualitatively explained by a sharp distance dependence of outer sphere (or solvent) reorganization energy, as predicted by Sutin and co-workers (J. Am. Chem. Soc.1984, 106, 6858), and almost distance-independent electronic couplings. Here, we report another example of such an underexplored behavior with three kinked D-B-A systems of rDA ∼ 10-19 Å, showing increasing rates of nonradiative charge recombination with increasing rDA. The three D-B-A systems are based on boron dipyrromethene and triphenylamine as electron acceptor and donor groups, respectively, with aryl bridges where the donor and acceptor moieties are connected at meso-positions. These D-B-A molecules exhibit radiative electron transfer reactions (or charge-transfer emission), which enables us to experimentally determine the solvent reorganization energy and the electronic couplings. The analysis of charge-transfer emission that explicitly considers electron-vibration coupling, in conjunction with the temperature-dependent analysis and computational method, revealed that the solvent reorganization energy indeed increases with distance, and at the same time, the electronic coupling decreases with distance expectedly. Therefore, under the right conditions for solvent reorganization energy and electronic coupling values, our results show that we can observe the acceleration of electron transfer reactions with increasing distance, even when we have the expected distance dependence of electronic coupling. This work indicates that the acceleration of electron transfer with increasing distance may be achieved with a fine-tuning of molecular design.

Anti-Kasha Fluorescence in Molecular Entities: Central Role of Electron-Vibrational Coupling.

According to Kasha's rule, the emission of a photon in a molecular system always comes from the lowest excited state. A corollary of this rule (i.e., the Kasha-Vavilov rule) states that the emission spectra are independent of the excitation wavelength. Although these rules apply for most of the molecular systems, violations of these rules are often reported. The prototypical case of a Kasha's rule violation is the fluorescence observed from S2 in azulene. Thanks to the advances in both theoretical and experimental research, other types of anomalous fluorescence (e.g., excitation energy transfer (EET)-based dual emissions, thermally activated fluorescence, etc.) are more recurrently reported in the literature. Sometimes, these anomalous processes involve higher-lying excited states but are mechanistically different from the azulene-like anomalous fluorescence. However, the underlying mechanisms leading to these anomalous emissions can be numerous and are not yet well understood.In order to shed some light on the above phenomena, this Account provides a comprehensive review of this topic. We herein report quantum chemical investigations in target molecular systems breaking Kasha's rule. The latter molecules were chosen because they were unambiguously reported to display anti-Kasha fluorescence. Our studies highlight three different types of anti-Kasha scenarios. Specifically, (i) the strong electronic, weak vibrational nonadiabatic coupling (NAC) regime (here named the type I case, i.e., azulene-like); (ii) the strong electronic, strong vibrational NAC regime (type II case, i.e., thermally activated S2 fluorescence); and the (iii) very weak electronic NAC regime (type III case, i.e., EET dyads). In addition, by combining state-of-the-art quantum chemical calculations with excited-state decay rate theories and appropriate excited-state kinetic models, we provide semiquantitative estimations of photoluminescence quantum yields for the most rigid molecular entities. Finally, we propose the use of simple theoretical descriptors relying on calculations of the excited-state density difference and the electron-vibrational coupling to classify anomalous emissions according to their coupling scenario.Besides the fundamental interest of the above investigations, the herein developed computational protocols and descriptors will be useful for the tailored design of dyes with tunable and unconventional fluorescence properties and their exploitation in a wide range of areas (i.e., from organic light-emitting diodes (OLEDs) to bioimaging, small-molecule fluorescent probes, and photocatalysis). Finally, our theoretical framework enables the attainment of a holistic understanding of the interconversion processes between excited states, where the electron-vibrational coupling is shown to play a central role in determining the efficacy.

Signatures of intramolecular vibrational and vibronic Q_{mathrm{x}}–Q_{mathrm{y}} coupling effects in absorption and CD spectra of chlorophyll dimers

An electron-vibrational coupling model that includes the vibronic (non-adiabatic) coupling between the Q_{mathrm{y}} and Q_{mathrm{x}} transitions of chlorophyll (Chl), created by Reimers and coworkers (Scientific Rep. 3, 2761, 2013) is extended here to chlorophyll dimers with interchlorophyll excitonic coupling. The model is applied to a Chl a dimer of the water-soluble chlorophyll binding protein (WSCP). As for isolated chlorophyll, the vibronic coupling is found to have a strong influence on the high-frequency vibrational sideband in the absorption spectrum, giving rise to a band splitting. In contrast, in the CD spectrum the interplay of vibronic coupling and static disorder leads to a strong suppression of the vibrational sideband in excellent agreement with the experimental data. The conservative nature of the CD spectrum in the low-energy region is found to be caused by a delicate balance of the intermonomer excitonic coupling between the purely electronic Q_{mathrm{y}} transition and the Q_{mathrm{y}} transition involving intramolecular vibrational excitations on one hand and the coupling to higher-energy electronic transitions on the other hand.

Influence of the electron-vibration coupling on the interfacial charge transfer in organic solar cells: a simple quantum model

In this paper, we analyze the influence of the electron-vibration interaction on the charge transfer process at the donor-acceptor interface in an organic solar cell. We present an essentially exact numerical analysis for a minimal model with only one vibration mode which is coupled to the charge transfer state. We show that the charge transfer state can be hot or cold depending on the parameters and in particular on the value of the energy of the lowest unoccupied molecular orbital on the donor side. We analyze also different regimes where electron–hole attraction or hybridization effects at the interface can modify the quantum yield of the transfer. We discuss also briefly the possible effects of the other vibration modes that are coupled to the charge either on the donor side or on the acceptor side.

Origin of Nonmonotonical Variation of Luminescence Efficiency under Pressure in Organic Molecule.

The nonmonotonical variation of luminescence efficiency under extra pressure occurs frequently in organic molecules; however, the mechanism behind this is still elusive. Using a theoretical protocol combining thermal vibration function rate formalism coupled quantum mechanics/molecular mechanics models, we explored the relationship between extra pressure, molecular packing, and fluorescent quantum efficiency (FQE) of the representative 1,2,3,4-tetraphenyl-1,3-cyclopentadiene (TPC). It is found that the first increase and then decrease of FQE in TPC crystalline aggregates upon pressurization is cooperatively attributed to the continuous reduction of the radiative decay rate constant and nonmonotonical change of the nonradiative decay rate constant (kic). The initial decrease of kic originates from the effective suppression of electron-vibration coupling and the Duschinsky rotation effect by extra pressure, whereas the following increase of kic comes from the surge of nonadiabatic electronic coupling and the reduction of adiabatic excitation energy upon further compression. This study can provide a theoretical basis for the rational design and performance control of the piezochromic luminescent materials.