Time-Dependent Density Matrix Renormalization Group Method for Quantum Transport with Phonon Coupling in Molecular Junction.

Quantum transport in molecular junctions has attracted great attention. The charge motion in a molecular junction can cause geometric deformation, leading to strong electron phonon coupling, which was often overlooked. We have formulated a nearly exact method to assess the time-dependent current and occupation number in the molecular junction modeled by the electron-phonon coupled bridge state using the time-dependent density matrix renormalization group (TD-DMRG) method. The oscillation period and amplitude of the current are found to be dependent on the electron phonon coupling strength and energy level alignment with the electrodes. In an attempt to better understand these phenomena, we have devised a new approximation that explains the bistability phenomenon and the behavior of steady currents in the strong electron-phonon coupling regime. Comparisons have been made with the multilayer-multiconfiguration time-dependent Hartree (ML-MCTDH) method and the analytical result in the purely electronic limit. Furthermore, we explore the entropy of different orderings, extending to the electron phonon model problems. Regarding finite temperature, the thermal Bogoliubov transformation of both fermions and bosons is used and compared with imaginary time evolution results.

Quantum Dynamical Approach to Predicting the Optical Pumping Threshold for Lasing in Organic Materials.

The quantum dynamic (QD) study of organic lasing (OL) is a challenging issue in organic optoelectronics. Previously, the phenomenological method has achieved success in describing experimental observation. However, it cannot directly bridge the laser threshold (LT) with microscopic parameters, which is the advantage of the QD method. In this paper, we propose a microscopic OL model and apply time-dependent wave packet diffusion to reveal the microscopic QD process of optically pumped lasing. LT is obtained from the onset of output as a function of optical input pumping. We predict that the LT has an optimal value as a function of the cavity volume and depends linearly on the intracavity photon leakage rate. The calculated structure-property relationships between molecular parameters and the LT are in qualitative agreement with the experimental results, confirming the reliability of our approach. This work is beneficial for understanding the OL mechanism and optimizing the design of organic laser materials.

Minimizing non-radiative decay in molecular aggregates through control of excitonic coupling.

The widely known "Energy Gap Law" (EGL) predicts a monotonically exponential increase in the non-radiative decay rate (knr) as the energy gap narrows, which hinders the development of near-infrared (NIR) emissive molecular materials. Recently, several experiments proposed that the exciton delocalization in molecular aggregates could counteract EGL to facilitate NIR emission. In this work, the nearly exact time-dependent density matrix renormalization group (TD-DMRG) method is developed to evaluate the non-radiative decay rate for exciton-phonon coupled molecular aggregates. Systematical numerical simulations show, by increasing the excitonic coupling, knr will first decrease, then reach a minimum, and finally start to increase to follow EGL, which is an overall result of two opposite effects of a smaller energy gap and a smaller effective electron-phonon coupling. This anomalous non-monotonic behavior is found robust in a number of models, including dimer, one-dimensional chain, and two-dimensional square lattice. The optimal excitonic coupling strength that gives the minimum knr is about half of the monomer reorganization energy and is also influenced by system size, dimensionality, and temperature.

TenCirChem: An Efficient Quantum Computational Chemistry Package for the NISQ Era.

TenCirChem is an open-source Python library for simulating variational quantum algorithms for quantum computational chemistry. TenCirChem shows high-performance in the simulation of unitary coupled-cluster circuits, using compact representations of quantum states and excitation operators. Additionally, TenCirChem supports noisy circuit simulation and provides algorithms for variational quantum dynamics. TenCirChem's capabilities are demonstrated through various examples, such as the calculation of the potential energy curve of H2O with a 6-31G(d) basis set using a 34-qubit quantum circuit, the examination of the impact of quantum gate errors on the variational energy of the H2 molecule, and the exploration of the Marcus inverted region for charge transfer rate based on variational quantum dynamics. Furthermore, TenCirChem is capable of running real quantum hardware experiments, making it a versatile tool for both simulation and experimentation in the field of quantum computational chemistry.

Unified Definition of Exciton Coherence Length for Exciton-Phonon Coupled Molecular Aggregates.

Exciton coherence length (ECL) characterizes the spatial extent of coherently delocalized excited states of molecular aggregates. Constructive/destructive superpositions of coherent molecular dipoles lead to superradiance/subradiance, where the radiative rate is enhanced/suppressed compared to that of a single molecule. Longer ECLs correspond to faster/slower radiative rates for superradiant/subradiant aggregates. However, previous ECL definitions fail to produce monotonic relationships when exciton-phonon coupling is considered, even for simple 1D exciton-phonon systems. This problem is exacerbated for 2D aggregates with both constructive and destructive superpositions. In this Letter, we propose a novel ECL definition by virtue of sum rule for oscillator strengths, ensuring a bijective and monotonic relationship between ECL and radiative rate for both 1D/2D superradiant and subradiant aggregates. Using numerically accurate time-dependent matrix product states, we study large-scale, exciton-phonon coupled 2D aggregates and predict the existence of maximum superradiance at finite temperature, in contrast to the previously believed 1/T law. Our results provide new insights into the design and optimization of efficient light emitting materials.

Molecular design of DBA-type five-membered heterocyclic rings to achieve 200% exciton utilization for electroluminescence.

Achieving high exciton utilization is a long-cherished goal in the development of organic light-emitting diode materials. Herein, a three-step mechanism is proposed to achieve 200% exciton utilization: (i) hot triplet exciton (T2) conversion to singlet S1; (ii) singlet fission from S1 into two T1; (iii) and then a Dexter energy transfer to phosphors. The requirement is that S1 should lie slightly lower than or close to T2 and twice as high as T1 in energy. For this, a scenario is put forward to design a series of donor-bridge-acceptor (DBA) type molecules with 2E(T1) ≤ E(S1) < E(T2), in which the Baird-type aromatic pyrazoline ring is used as a bridge owing to its stabilized T1 (1.30-1.74 eV) and different kinds of donors and acceptors are linked to the bridge for regulating S1 (2.35-3.87 eV) and T2 (2.44-3.96 eV). The ultrafast spectroscopy and sensitization measurements for one compound (TPA-DBPrz) fully confirm the theoretical predictions.

Computational Method for Evaluating the Thermoelectric Power Factor for Organic Materials Modeled by the Holstein Model: A Time-Dependent Density Matrix Renormalization Group Formalism.

Organic/polymeric materials are of emerging importance for thermoelectric conversion. The soft nature of these materials implies strong electron-phonon coupling, often leading to carrier localization. This poses great challenges for the conventional Boltzmann transport description based on relaxation time approximation and band structure calculations. In this work, combining the Kubo formula with the finite-temperature time-dependent density matrix renormalization group (FT-TD-DMRG) in the grand canonical ensemble, we developed a nearly exact algorithm to calculate the thermoelectric power factor PF = α2 σ, where α is the Seebeck coefficient and σ is the electrical conductivity, and apply the algorithm to Holstein Hamiltonian with electron-phonon coupling to model organic materials. Our algorithm can provide a unified description covering the weak coupling limit described by the bandlike Boltzmann transport to the strong coupling hopping limit.

Toward practical quantum embedding simulation of realistic chemical systems on near-term quantum computers.

Quantum computing has recently exhibited great potential in predicting chemical properties for various applications in drug discovery, material design, and catalyst optimization. Progress has been made in simulating small molecules, such as LiH and hydrogen chains of up to 12 qubits, by using quantum algorithms such as variational quantum eigensolver (VQE). Yet, originating from the limitations of the size and the fidelity of near-term quantum hardware, the accurate simulation of large realistic molecules remains a challenge. Here, integrating an adaptive energy sorting strategy and a classical computational method-the density matrix embedding theory, which respectively reduces the circuit depth and the problem size, we present a means to circumvent the limitations and demonstrate the potential of near-term quantum computers toward solving real chemical problems. We numerically test the method for the hydrogenation reaction of C6H8 and the equilibrium geometry of the C18 molecule, using basis sets up to cc-pVDZ (at most 144 qubits). The simulation results show accuracies comparable to those of advanced quantum chemistry methods such as coupled-cluster or even full configuration interaction, while the number of qubits required is reduced by an order of magnitude (from 144 qubits to 16 qubits for the C18 molecule) compared to conventional VQE. Our work implies the possibility of solving industrial chemical problems on near-term quantum devices.

Detuning Effects on the Reverse Intersystem Crossing from Triplet Exciton to Lower Polariton.

The lower polariton (LP) can reduce the energy barrier of the reverse intersystem crossing (rISC) process from T1 to harvest triplet energy for fluorescence. Based on a Tavis-Cummings model including both singlet and triplet excitons, both coupled with quantized photons, we derive here a comprehensive rISC rate formalism. We found that the latter consists of three contributions: the one originated from spin-orbit coupling as first obtained by Martinez-Martinez et al. ( J. Chem. Phys. 2019, 151, 054106), the one from light-matter coupling of Ou et al. ( J. Am. Chem. Soc. 2021, 143, 17786), and the cross-term first reported here. We apply the formalism to investigate the experimentally observed barrier-free rISC (BFrISC) process in cavity devices with DABNA-2 molecular thin film. We found it can be attributed to the detuning effect. The rISC rates can be increased by orders of magnitude through changing the detuning energy to realize the BFrISC process. In addition, the BFrISC rates exhibit a maximum as a function of the incident angle and the doping concentration. The formalism provides a solid ground for molecular design toward highly efficient cavity-promoted light-emitting materials.

The Variance of Photophysical Properties of Tetraphenylethene and Its Derivatives during Their Transitions from Dissolved States to Solid States.

The study of aggregation-induced emission luminogens (AIEgens) shows promising perspectives explored in lighting, optical sensors, and biological therapies. Due to their unique feature of intense emissions in aggregated solid states, it smoothly circumvents the weaknesses in fluorescent dyes, which include aggregation-caused quenching of emission and poor photobleaching character. However, our present knowledge of the AIE phenomena still cannot comprehensively explain the mechanism behind the substantially enhanced emission in their aggregated solid states. Herein, to systematically study the mechanism, the typical AIEgens tetraphenylethene (TPE) was chosen, to elucidate its photophysical properties, the TPE in THF/H2O binary solvents, TPE in THF solvents depending on concentration, and the following direct conversion from a dissolved state to a precipitated solid state were analyzed. Moreover, the TPE derivatives were also investigated to supply more evidence to better decipher the generally optical behaviors of TPE and its derivatives. For instance, the TPE derivative was homogeneously dispersed into tetraethyl orthosilicate to monitor the variance of photophysical properties during sol-gel processing. Consequently, TPE and its derivatives are hypothesized to abide by the anti-Kasha rule in dissolved states. In addition, the factors primarily influencing the nonlinear emission shifting of TPE and its derivatives are also discussed.

Hybrid Quantum-Classical Boson Sampling Algorithm for Molecular Vibrationally Resolved Electronic Spectroscopy with Duschinsky Rotation and Anharmonicity.

Using a photonic quantum computer for boson sampling has demonstrated a tremendous advantage over classical supercomputers. It is highly desirable to develop boson sampling algorithms for realistic scientific problems. In this work, we propose a hybrid quantum-classical sampling (HQCS) algorithm to calculate the optical spectrum for complex molecules considering Duschinsky rotation effects and anharmonicity. The classical sum-over-states method for this problem has a computational complexity that exponentially increases with system size. The HQCS algorithm creates an intermediate harmonic potential energy surface (PES) to bridge the initial and final PESs. The magnitude and sign of the overlap between the initial and the intermediate state are estimated by boson sampling and classical algorithms, respectively. The overlap between the intermediate and the final state is efficiently evaluated by classical algorithms. The feasibility of HQCS is demonstrated in calculations of the emission spectrum of a Morse model as well as the pyridine molecule.

On the fly swapping algorithm for ordering of degrees of freedom in density matrix renormalization group.

Density matrix renormalization group (DMRG) and its time-dependent variants have found widespread applications in quantum chemistry, includingab initioelectronic structure of complex bio-molecules, spectroscopy for molecular aggregates, and charge transport in bulk organic semiconductors. The underlying wavefunction ansatz for DMRG, matrix product state (MPS), requires mapping degrees of freedom (DOF) into a one-dimensional topology. DOF ordering becomes a crucial factor for DMRG accuracy. In this work, we propose swapping neighboring DOFs during the DMRG sweeps for DOF ordering, which we term 'on the fly swapping' (OFS) algorithm. We show that OFS is universal for both static and time-dependent DMRG with minimum computational overhead. Examples are given for one dimensional antiferromagnetic Heisenberg model,ab initioelectronic structure of N2molecule, and the S1/S2internal conversion dynamics of pyrazine molecule. It is found that OFS can indeed improve accuracy by finding better DOF ordering in all cases.

A Novel Strategy toward Thermally Activated Delayed Fluorescence from a Locally Excited State.

It is well-known that thermally activated delayed fluorescence (TADF) is always generated from charge-transfer (CT) excited states in donor-acceptor (D-A) systems, which limits its application owing to a slow radiative process and a small stimulated emission cross section. Herein, a design strategy is proposed for realizing TADF from a locally excited (LE) state without a typical donor-acceptor type structure through controlling the intersystem crossing (ISC) and reverse intersystem crossing (RISC) processes between the lowest excited singlet with LE character and higher triplet states. Using this strategy, a boron difluoride derivative is theoretically predicted and experimentally synthesized to exhibit locally excited TADF (LE-TADF) with a fairly large radiative rate of 1.12 × 108 s-1, extremely fast RISC rate of 5.09 × 1010 s-1, and a large stimulated emission cross section of 4.35 × 10-17 cm2, making this a promising organic amplified spontaneous emission (ASE) material. This work might open a new avenue to extend TADF materials, especially TADF laser emitters.

Heavy-Atom-Free Room-Temperature Phosphorescent Rylene Imide for High-Performing Organic Photovoltaics.

Organic phosphorescence, originating from triplet excitons, has potential for the development of new generation of organic optoelectronic materials. Herein, two heavy-atom-free room-temperature phosphorescent (RTP) electron acceptors with inherent long lifetime triplet exctions are first reported. These two 3D-fully conjugated rigid perylene imide (PDI) multimers, as the best nonfullerene wide-bandgap electron acceptors, exhibit a significantly elevated T1 of ≈2.1 eV with a room-temperature phosphorescent emission (τ = 66 µs) and a minimized singlet-triplet splitting as low as ≈0.13 eV. The huge spatial congestion between adjacent PDI skeleton endows them with significantly modified electronic characteristics of S1 and T1 . This feature, plus with the fully-conjugated rigid molecular configuration, balances the intersystem crossing rate and fluorescence/phosphorescence rates, and therefore, elevating ET1 to ≈2.1 from 1.2 eV for PDI monomer. Meanwhile, the highly delocalized feature enables the triplet charge-transfer excitons at donor-acceptor interface effectively dissociate into free charges, endowing the RTP electron acceptor based organic solar cells (OSCs) with a high internal quantum efficiency of 84% and excellent charge collection capability of 94%. This study introduces an alternative strategy for designing PDI derivatives with high-triplet state-energy and provides revelatory insights into the fundamental electronic characteristics, photophysical mechanism, and photo-to-current generation pathway.

A computational scheme for evaluating the phosphorescence quantum efficiency: applied to blue-emitting tetradentate Pt(II) complexes.

Phosphorescent organic light-emitting diodes (PhOLEDs) are leading candidates for displays or lighting technologies. Recently, blue phosphorescent tetradentate Pt(II) complexes have been attracting extensive attention due to their high phosphorescence quantum efficiency and numerous chemical structures on account of flexible ligand frames and modifications. Using quantum chemistry coupled with our thermal vibration correlation function (TVCF) formalism, we investigated the triplet excited state energy surface and the decay processes involving both direct vibrational relaxation and minimum energy crossing point (MECP) via the transition state (3TS) to the ground state (S0) for 16 recently experimentally reported blue-emitting tetradentate Pt(II) emitters containing fused 5/6/6 metallocycles. We found that (i) in most cases, the direct vibrational relaxation deactivations dominated the triplet non-radiative decay because either the 3TS is too high or the MECP is not reachable. Hence, results from the TVCF formalism agreed well with the experiments for the phosphorescence quantum efficiency; (ii) only when both 3TS and MECP are low, for instance, for PtON1-oMe, deactivations via MECP dominated the triplet non-radiative decay.

Catechol Moiety Integrated Tri-Aryl Type AIEgen for Visual and Quantitative Boronic Acid Detection.

Novel functional AIEgen based on three compact bound aryl skeletons is designed and synthesized. This tri-aryl type luminogen (TA-Catechol) embedded with catechol moiety responds rapidly to series of boronic acids. Real-time visual and quantitative dual-mode detection method is established for the first time with modest precision and low detection limit (8.0 µM). Detailed mechanistic discussion identifies tetra-coordinated boronic species as the key intermediate within sensing procedure. Wide range of organic boronic acids compatible with this strategy is displayed which is promising in high throughput screening technology. Furthermore, solid-state sensing capability of TA-Catechol is also demonstrated.

Sunlight-Coordinated High-Performance Moisture Power in Natural Conditions.

It is a challenge to spontaneously harvest multiple clean sources from the environment for upgraded energy-converting systems. The ubiquitous moisture and sunlight in nature are attractive for sustainable power generation especially. A high-performance light-coordinated "moist-electric generator" (LMEG) based on the rational combination of a polyelectrolyte and a phytochrome is herein developed. By spontaneous adsorption of gaseous water molecules and simultaneous exposure to sunlight, a piece of 1 cm2 composite film offers an open-circuit voltage of 0.92 V and a considerable short-circuit current density of up to 1.55 mA cm-2 . This record-high current density is about two orders of magnitude improvement over that of most conventional moisture-enabled systems, which is caused by moisture-induced charge separation accompanied with photoexcited carrier migration, as confirmed by a dynamic Monte Carlo device simulation. Flexible devices with customizable size are available for large-scale integration to effectively work under a wide range of relative humidity (about 20-100%), temperature (10-80 °C), and light intensity (30-200 mW cm-2 ). The wearable and portable LMEGs provide ample power supply in natural conditions for indoor and outdoor electricity-consuming systems. This work opens a novel avenue to develop sustainable power generation through collecting multiple types of natural energy by a single hybrid harvester.

Effect of Strong Intermolecular Interaction in 2D Inorganic Molecular Crystals.

Strong intermolecular interactions in 2D organic molecular crystals arising from π-π stacking have been widely explored to achieve high thermal stability, high carrier mobility, and novel physical properties, which have already produced phenomenal progress. However, strong intermolecular interactions in 2D inorganic molecular crystals (2DIMCs) have rarely been investigated, severely limiting both the fundamental research in molecular physics and the potential applications of 2DIMCs for optoelectronics. Here, the effect of strong intermolecular interactions induced by unique short intermolecular Se-Se and P-Se contacts in 2D α-P4Se3 nanoflakes is reported. On the basis of theoretical calculations of the charge density distribution and an analysis of the thermal expansion and plastic-crystal transition, the physical picture of strong intermolecular interactions can be elucidated as a higher charge density between adjacent P4Se3 molecules, arising from an orderly and close packing of P4Se3 molecules. More importantly, encouraged by the strong intermolecular coupling, the in-plane mobility of α-P4Se3 nanoflakes is first calculated with a quantum nuclear tunneling model, and a competitive hole mobility of 0.4 cm2 V-1 s-1 is obtained. Our work sheds new light on the intermolecular interactions in 2D inorganic molecular crystals and is highly significant for promoting the development of molecular physics and optoelectronics.

Enhanced Reverse Intersystem Crossing Promoted by Triplet Exciton-Photon Coupling.

Polaritons are hybrid light-matter states formed via strong coupling between excitons and photons inside a microcavity, leading to upper and lower polariton (LP) bands splitting from the exciton. The LP has been applied to reduce the energy barrier of the reverse intersystem crossing (rISC) process from T1, harvesting triplet energy for fluorescence through thermally activated delayed fluorescence. The spin-orbit coupling between T1 and the excitonic part of the LP was considered as the origin for such an rISC transition. Here we propose a mechanism, namely, rISC promoted by the light-matter coupling (LMC) between T1 and the photonic part of LP, which is originated from the ISC-induced transition dipole moment of T1. This mechanism was excluded in previous studies. Our calculations demonstrate that the experimentally observed enhancement to the rISC process of the erythrosine B molecule can be effectively promoted by the LMC between T1 and a photon. The proposed mechanism would substantially broaden the scope of the molecular design toward highly efficient cavity-promoted light-emitting materials and immediately benefit the illumination of related experimental phenomena.