Electron-vibration Interaction Research Articles

Positional Isomerism of Aromatic Heterocyclic Spacer Cations in Two-Dimensional Dion-Jacobson Hybrid Perovskites.

Ligand engineering of aromatic heterocyclic cations in two-dimensional (2D) Dion-Jacobson (DJ) perovskites has been widely explored in recent years. In this study, how the positional isomers of aromatic heterocyclic cations tune the lattice of 2D perovskites, thereby influencing the transport and recombination dynamics of charge carriers, has been investigated through nonadiabatic molecular dynamics simulations. We demonstrate that the meta-substituted 3-(aminomethyl)pyridinium (3AMPY) cations greatly reduce the strength of electron-vibration coupling since the strong hydrogen-bonding network introduced by the changes in the arrangement of spacer cations significantly suppresses the structural thermal fluctuations. Compared to the para-substituted 4-(aminomethyl)pyridinium (4AMPY) cation, using the asymmetric 3AMPY as a spacer cation can achieve improved in-plane transport performance, enhanced thermal stability, and suppressed charge carrier recombination through weakening electron-vibration interactions. Our results explain the observed lifetime difference between the two types of DJ-phase perovskites in experiments and provide new guidance for optimizing the performance of perovskite devices.

Accelerated Electron-Hole Separation at the Organic-Inorganic Anthracene/Janus MoSSe Interface.

Organic light-absorbing materials with two-dimensional semiconductor layers as contact electrodes are promising for efficient and flexible low-cost solar cells. Considering anthracene as an absorber and a MoSSe Janus monolayer, we use non-adiabatic molecular dynamics to show that electron transfer from anthracene to MoSSe is faster on the Se side than the S side. The transfer from anthracene to MoS2 and MoSe2 monolayers takes intermediate times. As a rule, we find that a shorter adsorption distance produces a stronger donor-acceptor coupling. The smaller distance on the Se side is rationalized by the attractive force between the intrinsic dipole moment of the Janus structure and that of the molecule induced due to adsorption. Quantum coherence also affects the transfer time. The study provides detailed insights into adsorption of molecules on Janus structures and the resulting electronic and electron vibrational interactions. The results suggest that the dipole interaction plays an important role in the thermodynamic stability, alignment of electronic levels, and electron vibrational dynamics.

Electronic dynamics through conical intersections via non-Markovian stochastic Schrödinger equation with complex modes.

Conical intersections (CIs) play a crucial role in photochemical reactions, offering an efficient channel for ultrafast non-adiabatic relaxation of excited states. This significantly influences the reaction pathways and the resulting products. In this work, we utilize the non-Markovian stochastic Schrödinger equation with complex modes method to explore the dynamics of electronic transitions through conical intersections (CIs) in pyrazine. The linear vibronic coupling model serves as the foundational framework, incorporating both intra-state and inter-state electron-vibrational interactions. The dynamics of the excited electronic transitions are analyzed across varying strengths of system-bath coupling and different bath relaxation times. The accuracy of this method is demonstrated by comparing its predictions with those from the hierarchical equations of motion method.

Strain-Phonon Cooperation as a Necessary Ingredient to Understand the Jahn-Teller Effect in Solids.

Spatial degeneracy is the cause of the complex electronic, geometrical, and magnetic structures found in a number of materials whose more representative example is KCuF3. In the literature the properties of this lattice are usually explained through the Kugel--Khomskii model, based on superexchange interactions. Here we provide rigorous theoretical and computational arguments against this view proving that structural and magnetic properties essentially arise from electron-vibration (vibronic) interactions. Moreover, based on the work of Öpik and Pryce, we show that the coupling between lattice (homogeneous strain) and motif (phonons) distortions is essential to understand the main stable configurations of the lattice. Using this information, we predict a new low-energy phase in KCuF3 that could strongly alter its properties and provide guidance on how to stabilize it through strain engineering.

Nonadiabatic dynamics of molecules interacting with metal surfaces: A quantum-classical approach based on Langevin dynamics and the hierarchical equations of motion.

A novel mixed quantum-classical approach to simulating nonadiabatic dynamics of molecules at metal surfaces is presented. The method combines the numerically exact hierarchical equations of motion approach for the quantum electronic degrees of freedom with Langevin dynamics for the classical degrees of freedom, namely, low-frequency vibrational modes within the molecule. The approach extends previous mixed quantum-classical methods based on Langevin equations to models containing strong electron-electron or quantum electronic-vibrational interactions, while maintaining a nonperturbative and non-Markovian treatment of the molecule-metal coupling. To demonstrate the approach, nonequilibrium transport observables are calculated for a molecular nanojunction containing strong interactions.

Lattice dynamics and self-trapped excitons in the Cs2SnBr6 double perovskites

Our study delved into the detailed investigation of Cs2SnBr6 double perovskites, focusing on their electrical properties, lattice dynamics, and stability. The direct bandgap for Cs2SnBr6 was estimated to be at 2.93 eV. One external translational mode of the Cs+ lattice with T 2g symmetry and three internal modes of the octahedral with A 1g, E g, and T 2g symmetries are defined by calculated lattice dynamics, experimental micro-Raman scattering. We show a correlation with first-principles calculations, validating using a band-structured electronic approach to understanding the behavior of charge carriers, and electron–phonon interactions in Cs2SnBr6. We propose that electron-vibration interactions result in self-trapped excitons (STEs) displaying significant Stokes shifts (0.508 eV) and broad-spectrum emission. Understanding the behavior of STEs is fundamental for their optoelectronic applications.

Impact of large A-site cations on electron-vibrational interactions in 2D halide perovskites: Ab initio quantum dynamics.

Using abinitio nonadiabatic molecular dynamics, we study the effect of large A-site cations on nonradiative electron-hole recombination in two-dimensional Ruddlesden-Popper perovskites HA2APb2I7, HA = n-hexylammonium, A = methylammonium (MA), or guanidinium (GA). The steric hindrance created by large GA cations distorts and stiffens the inorganic Pb-I lattice, reduces thermal structural fluctuations, and maintains the delocalization of electrons and holes at ambient and elevated temperatures. The delocalized charges interact more strongly in the GA system than in the MA system, and the charge recombination is accelerated. In contrast, replacement of only some MA cations with GA enhances disorder and increases charge lifetime, as seen in three-dimensional perovskites. This study highlights the key influence of structural fluctuations and disorder on the properties of charge carriers in metal halide perovskites, providing guidance for tuning materials' optoelectronic performance.

Nuclear Quantum Effects Prolong Charge Carrier Lifetimes in Hybrid Organic-Inorganic Perovskites.

Hybrid organic-inorganic perovskites (HOIPs) contain light hydrogen atoms that exhibit significant nuclear quantum effects (NQEs). We demonstrate that NQEs have a strong effect on HOIP geometry and electron-vibrational dynamics at both low and ambient temperatures, even though charges in HOIPs reside on heavy elements. By combining ring-polymer molecular dynamics (MD) and ab initio MD with nonadiabatic MD and time-dependent density functional theory and focusing on the most studied tetragonal CH3NH3PbI3, we show that NQEs increase the disorder and thermal fluctuations through coupling of the light inorganic cations to the heavy inorganic lattice. The additional disorder induces charge localization and decreases electron-hole interactions. As a result, the nonradiative carrier lifetimes are extended by a factor of 3 at 160 K and 1/3 at 330 K. The radiative lifetimes are increased by 40% at both temperatures. The fundamental band gap decreases by 0.10 and 0.03 eV at 160 and 330 K, respectively. By enhancing atomic motions and introducing new vibrational modes, NQEs strengthen electron-vibrational interactions. Decoherence, determined by elastic scattering, accelerates almost by a factor of 2 due to NQEs. However, the nonadiabatic coupling, driving nonradiative electron-hole recombination, decreases because it is more sensitive to structural distortions than atomic motions in HOIPs. This study demonstrates, for the first time, that NQEs should be considered to achieve an accurate understanding of geometry evolution and charge carrier dynamics in HOIPs and provides important fundamental insights for the design of HOIPs and related materials for optoelectronic applications.

Extended-charge-transfer excitations in crystalline non-fullerene acceptors

In organic solar cells with non-fullerene acceptors (NFAs), an intra-moiety excited state, originating from intermolecular interactions in the acceptor domain, acts as a key immediate for charge separation. However, the nature of the intra-moiety state remains elusive. Here, we employ a model Hamiltonian with parameters derived from a model system of Y6 crystal to study the nature of low-lying excited states in NFAs. We find the intra-moiety excited state is mixed with local excitation and charge-transfer excitation (CTE) characters with nonnegligible contributions from extended CTEs with spatially-separated electrons and holes. The spatial extent of such a loosely bound state is susceptible to the intermolecular electronic interaction and electron–vibration interaction, which may be promoted by molecule engineering and morphology control. The findings provide an alternative strategy towards device optimization by manipulating the delocalization of intra-moiety state in organic photovoltaic materials.

Bioexcitons by Design: How Do We Get There?

Biological pigment-protein complexes (PPCs) exhibit a remarkable ability to tune the optical properties of biological excitons (bioexcitons) through specific pigment-protein interactions. While such fine-tuning allows natural systems (e.g., photosynthetic proteins) to carry out their native functions with near-optimal performance, native function itself is often suboptimal for applications such as biofuel production or quantum technology development. This perspective offers a look at near-term prospects for the rational reoptimization of PPC bioexcitons for new functions using site-directed mutagenesis. The primary focus is on the "structure-spectrum" challenge of understanding the relationships between structural features and spectroscopic properties. While recent examples demonstrate that site-directed mutagenesis can be used to tune nearly all key bioexciton parameters (e.g., site energies, interpigment couplings, and electronic-vibrational interactions), critical challenges remain before we achieve truly rational design of bioexciton properties.

Optomechanical effects in nanocavity-enhanced resonant Raman scattering of a single molecule

In this article, we address the optomechanical effects in surface-enhanced resonant Raman scattering (SERRS) from a single molecule in a nano-particle on mirror (NPoM) nanocavity by developing a quantum master equation theory, which combines macroscopic quantum electrodynamics and electron-vibration interaction within the framework of open quantum system theory. We supplement the theory with electromagnetic simulations and time-dependent density functional theory calculations in order to study the SERRS of a methylene blue molecule in a realistic NPoM nanocavity. The simulations allow us not only to identify the conditions to achieve conventional optomechanical effects, such as vibrational pumping, non-linear scaling of Stokes and anti-Stokes scattering, but also to discovery distinct behaviors, such as the saturation of exciton population, the emergence of Mollow triplet side-bands, and higher-order Raman scattering. All in all, our study might guide further investigations of optomechanical effects in resonant Raman scattering.

Electronic–Vibrational Resonance Does Not Significantly Alter Steady-State Transport in Natural Light-Harvesting Systems

Oscillations in time-dependent two-dimensional electronic spectra appear as evidence of quantum coherence in light-harvesting systems related to electronic-vibrational resonant interactions. Nature, however, takes place in a non-equilibrium steady-state; therefore, the relevance of these arguments to the natural process is unclear. Here, we examine the role of intramolecular vibrations in the non-equilibrium steady-state of photosynthetic dimers in the natural scenario of incoherent light excitation. Specifically, we analyze the PEB dimer in the cryptophyte algae PE545 antenna protein. It is found that vibrations resonant with the energy difference between exciton states only marginally increase the quantum yield and the imaginary part of the intersite coherence that is relevant for transport compared to non-resonant vibrations in the natural non-equilibrium steady-state. That is, the electronic-vibrational resonance interaction does not significantly enhance energy transport under natural incoherent light excitation conditions.

Mixed Sulfur/Selenium Anions Weaken Electron-Vibrational Interaction in Cu2ZnSn(S,Se)4 Photoabsorber

Kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar absorbers have attracted intensive investigations for next-generation photovoltaic applications. Here, by using ab initio static and molecular dynamics simulations, we investigated the anion compositional dependence of electron-vibration interaction in CZTSSe materials. We found that the conduction band fluctuates more than the valence band, and as a result, the band gap variation is more sensitive to the change of the former, which can be understood in terms of p-d hybridization in the valence bands. Electron-phonon coupling is smaller in CZTSSe alloy compared to pure S- or Se-containing structures, as evidenced by the smaller fluctuation of excitation energy, and can be attributed to the weaker structural dynamics of the metal-anion bond. Small electron-phonon coupling strength may lead to better charge transport in these materials. We also elucidated the interplay between disordered structures and S/Se stoichiometry through analysis of optical line width. The results highlight the importance of anion composition engineering and provide new insights into the rational design of high-performing kesterite absorbers for solar cells.

Minimal model of excited-state symmetry breaking in symmetric dimers and covalently linked dyads.

A model of symmetry breaking (SB) charge separation in symmetric excited dyads and dimers is presented. The minimal model should include at least four basis electronic states due to a small energy gap between the locally excited and charge separated (zwitterionic) states of the chromophores. There are electronic couplings between all these states. The model includes the following interactions: (i) the Coulomb interaction between charges on the chromophores of the dyad, (ii) the interaction of the dipole moment of the asymmetric dyad with the solvent polarization, and (iii) the electronic-vibrational interaction. SB becomes possible only if the intensity of these interactions exceeds a threshold value. The threshold vanishes if there is a degeneration of the levels. Unusual resonant dependencies of the dissymmetry degree on the model parameters are revealed. Resonances arise due to the degeneration of energy levels. The ranges of the parameters in which energy level crossings occur are established. The oddity lies in the dependence of the resonance shape on the parameters of the model. A variation in the electronic couplings and the energy gap between the locally excited and ionic states, which leads to a broadening of the resonance, simultaneously leads to an increase in the resonant height. This opens up wide possibilities for controlling the charge separation degree. The predictions of the theory agree with the available experimental data. The charge separation SB is predicted to accompany by SB in the excitation distribution on the branches of dyads.

Structural Disorder in Higher-Temperature Phases Increases Charge Carrier Lifetimes in Metal Halide Perovskites.

Solar cells and optoelectronic devices are exposed to heat that degrades performance. Therefore, elucidating temperature-dependent charge carrier dynamics is essential for device optimization. Charge carrier lifetimes decrease with temperature in conventional semiconductors. The opposite, anomalous trend is observed in some experiments performed with MAPbI3 (MA = CH3NH3+) and other metal halide perovskites. Using ab initio quantum dynamics simulation, we establish the atomic mechanisms responsible for nonradiative electron-hole recombination in orthorhombic-, tetragonal-, and cubic MAPbI3. We demonstrate that structural disorder arising from the phase transitions is as important as the disorder due to heating in the same phase. The carrier lifetimes grow both with increasing temperature in the same phase and upon transition to the higher-temperature phases. The increased lifetime is rationalized by structural disorder that induces partial charge localization, decreases nonadiabatic coupling, and shortens quantum coherence. Inelastic and elastic electron-vibrational interactions exhibit opposite dependence on temperature and phase. The partial disorder and localization arise from thermal motions of both the inorganic lattice and the organic cations and depend significantly on the phase. The structural deformations induced by thermal fluctuations and phase transitions are on the same order as deformations induced by defects, and hence, thermal disorder plays a very important role. Since charge localization increases carrier lifetimes but inhibits transport, an optimal regime maximizing carrier diffusion can be designed, depending on phase, temperature, material morphology, and device architecture. The atomistic mechanisms responsible for the enhanced carrier lifetimes at elevated temperatures provide guidelines for the design of improved solar energy and optoelectronic materials.

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.

Effects of Electron-Vibration Interaction in Polariton Luminescence: Non-Markovian Fano Resonances and Hot Luminescence.

We have developed a non-Markovian theory of the polariton luminescence taking the molecular vibrations into account. The calculations were performed in the polariton basis. We have shown that the frequency shift and the polariton spectral line broadening strongly depend on the frequency-dependent exciton contribution to the polariton. In the single-mode microcavity, our non-Markovian theory predicts the Fano resonances in the polariton luminescence and also narrowing of the spectral lines with the increase of the total number of molecules in the case of the intramolecular nature of the low-frequency vibrations. The theory enables us to consider a nonequilibrium (hot) exciton-polariton luminescence similar to the hot luminescence of molecules and crystals. This opens a way for its observation in organic-based nanodevices.

Site Occupancies, Electron-Vibration Interaction and Energy Transfer of CaMgSi2 O6 : Eu2+ , Mn2+ Phosphors for Potential Temperature-Sensing and Anti-counterfeiting Applications.

Eu2+ -, Mn2+ - and Eu2+ -Mn2+ -doped CaMgSi2 O6 phosphors have been prepared by a high-temperature solid-state reaction. Systematic investigation of the concentration- and temperature-dependent luminescence of Mn2+ showed that Mn2+ ions occupy two distinct sites in CaMgSi2 O6 . Electron-vibration interaction (EVI) analyses of Mn2+ ions revealed Huang-Rhys factors of 4.73 and 2.82 as well as effective phonon energies of 313 and 383 cm-1 for the two sites. Eu2+ -Mn2+ energy transfer is also discussed, and its efficiency is estimated by lifetime and luminescence spectra. The different thermal quenching behaviours of Eu2+ and Mn2+ , the distinct emission colours of Eu2+ (blue, band peak at ∼451 nm) and Mn2+ (yellow-red range, band peaks at ∼583 and 693 nm) endow the co-doped samples with potential applications in luminescence thermometry and temperature-/excitation wavelength-responsive dual anti-counterfeiting.

Charge and Spin Dynamics and Enantioselectivity in Chiral Molecules.

Charge and spin dynamics are addressed in chiral molecules immediately after their instantaneous coupling to an external metallic reservoir. This work describes how a spin polarization is induced in the chiral structure as a response to the charge dynamics. The dynamics indicate that chiral induced spin selectivity is an excited state phenomenon that in the transient regime can be partly captured using a simplistic single-particle description but in the stationary limit definitively shows that electron correlations, e.g., electron–vibration interactions, crucially contribute to sustain an intrinsic spin anisotropy that can lead to a nonvanishing spin selectivity. The dynamics, moreover, provide insight into enantiomer separation, due to different acquired spin polarizations.

Stochastic Adaptive Single-Site Time-Dependent Variational Principle.

In recent years, the time-dependent variational principle (TDVP) method based on the matrix product state (MPS) wave function formulation has shown its great power in performing large-scale quantum dynamics simulations for realistic chemical systems with strong electron–vibration interactions. In this work, we propose a stochastic adaptive single-site TDVP (SA-1TDVP) scheme to evolve the bond-dimension adaptively, which can integrate the traditional advantages of both the high efficiency of the single-site TDVP (1TDVP) variant and the high accuracy of the two-site TDVP (2TDVP) variant. Based on the assumption that the level statistics of entanglement Hamiltonians, which originate from the reduced density matrices of the MPS method, follows a Poisson or Wigner distribution, as generically predicted by random-matrix theory, additional random singular values are generated to expand the bond-dimension automatically. Tests on simulating the vibrationally resolved quantum dynamics and absorption spectra in the pyrazine molecule and perylene bisimide (PBI) J-aggregate trimer as well as a spin-1/2 Heisenberg chain show that it can be automatic and as accurate as 2TDVP but reduce the computational time remarkably.