Unlocking the NIR-II AIEgen for High Brightness through Intramolecular Electrostatic Locking.

Fluorescent imaging and biosensing in the near-infrared-II (NIR-II) window holds great promise for non-invasive, radiation-free, and rapid-response clinical diagnosis. However, it's still challenging to develop bright NIR-II fluorophores. In this study, we report a new strategy to enhance the brightness of NIR-II aggregation-induced emission (AIE) fluorophores through intramolecular electrostatic locking. By introducing sulfur atoms into the side chains of the thiophene bridge in TSEH molecule, the molecular motion of the conjugated backbone can be locked through intramolecular interactions between the sulfur and nitrogen atoms. This leads to enhanced NIR-II fluorescent emission of TSEH in both solution and aggregation states. Notably, the encapsulated nanoparticles (NPs) of TSEH show enhanced brightness, which is 2.6-fold higher than TEH NPs with alkyl side chains. The in vivo experiments reveal the feasibility of TSEH NPs in vascular and tumor imaging with a high signal-to-background ratio and precise resection for tiny tumors. In addition, polystyrene nanospheres encapsulated with TSEH are utilized for antigen detection in lateral flow assays, showing a signal-to-noise ratio 1.9-fold higher than the TEH counterpart in detecting low-concentration antigens. This work highlights the potential for developing bright NIR-II fluorophores through intramolecular electrostatic locking and their potential applications in clinical diagnosis and biomedical research.

An endogenous promoter LpSUT2 discovered in duckweed: a promising transgenic tool for plants.

Promoters are one of the most critical elements in regulating gene expression. They are considered essential biotechnological tools for heterologous protein production. The one most widely used in plants is the 35S promoter from cauliflower mosaic virus. However, our study for the first time discovered the 35S promoter reduced the expression of exogenous proteins under increased antibiotic stress. We discovered an endogenous strong promoter from duckweed named LpSUT2 that keeps higher initiation activity under antibiotic stress. Stable transformation in duckweed showed that the gene expression of eGFP in the LpSUT2:eGFP was 1.76 times that of the 35S:eGFP at 100 mg.L-1 G418 and 6.18 times at 500 mg.L-1 G418. Notably, with the increase of G418 concentration, the gene expression and the fluorescence signal of eGFP in the 35S:eGFP were weakened, while the LpSUT2:eGFP only changed slightly. This is because, under high antibiotic stress, the 35S promoter was methylated, leading to the gene silencing of the eGFP gene. Meanwhile, the LpSUT2 promoter was not methylated and maintained high activity. This is a previously unknown mechanism that provides us with new insights into screening more stable promoters that are less affected by environmental stress. These outcomes suggest that the LpSUT2 promoter has a high capacity to initiate the expression of exogenous proteins. In conclusion, our study provides a promoter tool with potential application for plant genetic engineering and also provides new insights into screening promoters.

Ultra-photostable small-molecule dyes facilitate near-infrared biophotonics.

Long-wavelength, near-infrared small-molecule dyes are attractive in biophotonics. Conventionally, they rely on expanded aromatic structures for redshift, which comes at the cost of application performance such as photostability, cell permeability, and functionality. Here, we report a ground-state antiaromatic strategy and showcase the concise synthesis of 14 cationic aminofluorene dyes with mini structures (molecular weights: 299-504 Da) and distinct spectra covering 700-1600 nm. Aminofluorene dyes are cell-permeable and achieve rapid renal clearance via a simple 44 Da carboxylation. This accelerates optical diagnostics of renal injury by 50 min compared to existing macromolecular approaches. We develop a compact molecular sensing platform for in vivo intracellular sensing, and demonstrate the versatile applications of these dyes in multispectral fluorescence and optoacoustic imaging. We find that aromaticity reversal upon electronic excitation, as indicated by magnetic descriptors, not only reduces the energy bandgap but also induces strong vibronic coupling, resulting in ultrafast excited-state dynamics and unparalleled photostability. These results support the argument for ground-state antiaromaticity as a useful design rule of dye development, enabling performances essential for modern biophotonics.

Deprotonated sulfamic acid and its homodimers: Does sulfamic acid adopt zwitterion during cluster growth?

We present a joint experimental and computational study on the geometric and electronic structures of deprotonated sulfamic acid (SA) clusters [(SA)n-H]- (n = 1, 2) employing negative ion photoelectron spectroscopy and high-level ab initio calculations. The photoelectron spectra provide the vertical/adiabatic detachment energy (VDE/ADE) of the sulfamate anion (SM-) H2N●SO3- at 4.85 ± 0.05 and 4.58 ± 0.08 eV, respectively, and the VDE and ADE of the SM-●SA dimer at 6.41 ± 0.05 and 5.87 ± 0.08 eV, respectively. The significantly increased electron binding energies of the dimer confirm the enhanced electronic stability upon the addition of one SA molecule. The CCSD(T)-predicted VDEs/ADEs agree excellently with the experimental data, confirming the identified structures as the most stable ones. Two types of dimer isomers possessing different hydrogen bonding (HB) motifs are identified, corresponding to SM- binding to a zwitterionic SA (SM-●SAz) and a canonical SA (SM-●SAc), respectively. Two N-H⋯O HBs and one superior O-H⋯O HB are formed in the lowest-lying SM-●SAc, while SM-●SAz has three moderate N-H⋯O HBs, with the former being 4.71 kcal/mol more stable. Further theoretical analyses reveal that the binding strength advantage of SM-●SAc over SM-●SAz arises from its significant contributions of orbital interactions between fragments, illustrating that sulfamate strongly interacts with its parent SA acid and preferably chooses the canonical SA in the subsequent cluster formations. Given the prominent presence of SA, this study provides the first evidence that the canonical dimer model of sulfamic acid should exist as a superior configuration during cluster growth.

Observation of a super-tetrahedral cluster of acetonitrile-solvated dodecaborate dianion via dihydrogen bonding.

We launched a combined negative ion photoelectron spectroscopy and multiscale theoretical investigation on the geometric and electronic structures of a series of acetonitrile-solvated dodecaborate clusters, i.e., B12H122-·nCH3CN (n = 1-4). The electron binding energies of B12H122-·nCH3CN are observed to increase with cluster size, suggesting their enhanced electronic stability. B3LYP-D3(BJ)/ma-def2-TZVP geometry optimizations indicate each acetonitrile molecule binds to B12H122- via a threefold dihydrogen bond (DHB) B3-H3 ⁝⁝⁝ H3C-CN unit, in which three adjacent nucleophilic H atoms in B12H122- interact with the three methyl hydrogens of acetonitrile. The structural evolution from n = 1 to 4 can be rationalized by the surface charge redistributions through the restrained electrostatic potential analysis. Notably, a super-tetrahedral cluster of B12H122- solvated by four acetonitrile molecules with 12 DHBs is observed. The post-Hartree-Fock domain-based local pair natural orbital- coupled cluster singles, doubles, and perturbative triples [DLPNO-CCSD(T)] calculated vertical detachment energies agree well with the experimental measurements, confirming the identified isomers as the most stable ones. Furthermore, the nature and strength of the intermolecular interactions between B12H122- and CH3CN are revealed by the quantum theory of atoms-in-molecules and the energy decomposition analysis. Ab initio molecular dynamics simulations are conducted at various temperatures to reveal the great kinetic and thermodynamic stabilities of the selected B12H122-·CH3CN cluster. The binding motif in B12H122-·CH3CN is largely retained for the whole halogenated series B12X122-·CH3CN (X = F-I). This study provides a molecular-level understanding of structural evolution for acetonitrile-solvated dodecaborate clusters and a fresh view by examining acetonitrile as a real hydrogen bond (HB) donor to form strong HB interactions.

Locking water molecules via ternary O-H⋯O intramolecular hydrogen bonds in perhydroxylated closo-dodecaborate.

A multitude of applications related to perhydroxylated closo-dodecaborate B12(OH)122- in the condensed phase are inseparable from the fundamental mechanisms underlying the high water orientation selectivity based on the base B12(OH)122-. Herein, we directly compare the structural evolution of water clusters, ranging from monomer to hexamer, oriented by functional groups in the bases B12H122-, B12H11OH2- and B12(OH)122- using multiple theoretical methods. A significant revelation is made regarding B12(OH)122-: each additional water molecule is locked into the intramolecular hydrogen bond B-O-H ternary ring in an embedded form. This new pattern of water cluster growth suggests that B-(H-O)⋯H-O interactions prevail over the competition from water-hydrogen bonds (O⋯H-O), distinguishing it from the behavior observed in B12H122- and B12H11OH2- bases, in which competition arises from a mixed competing model involving dihydrogen bonds (B-H⋯H-O), conventional hydrogen bonds (B-(H-O)⋯H-O) and water hydrogen bonds (O⋯H-O). Through aqueous solvation and ab initio molecular dynamics analysis, we further demonstrate the largest water clusters in the first hydrated shell with exceptional thermodynamic stability around B12(OH)122-. These findings provide a solid scientific foundation for the design of boron cluster chemistry incorporating hydroxyl-group-modified borate salts with potential implications for various applications.

Beyond Duality: Rationalizing Repulsive Coulomb Barriers in Host-Guest Cyclodextrin-Dodecaborate Complexes.

The repulsive Coulomb barrier (RCB), an intrinsic potential energy barrier along electron detachment or charge-separation coordinates in multiply charged anions (MCAs), provides dynamic stability to MCAs whose electronic and thermodynamic stabilities are largely dictated by strong internal Coulomb repulsions. Spectroscopic and theoretical characterizations of the RCB have been focused on isolated MCAs. In this work, we extend the RCB investigation beyond the previous scope by including noncovalent host-guest cyclodextrin-closo-dodecaborate dianionic complexes χCD·B12X122- (χ = α, ß, γ; X = H, F-I). Photodechment photoelectron spectroscopy reveals the existence of two distinctly different RCBs, derived from detaching electrons from the guest dianions (RCB1) or ionizing the host neutrals (RCB2), respectively, with the latter being substantially smaller than the former. Theoretical calculations support the duality of RCBs in these complexes and further exhibit highly anisotropic nature of the RCBs.

Rigid and Photostable Shortwave Infrared Dye Absorbing/Emitting beyond 1200 nm for High-Contrast Multiplexed Imaging.

The shortwave infrared (SWIR) spectral region beyond 1200 nm offers optimal tissue penetration depth and has broad potential in diagnosis, therapy, and surgery. Here, we devised a novel class of fluorochromic scaffold, i.e., a tetra-benzannulated xanthenoid (EC7). EC7 absorbs/emits maximally at 1204/1290 nm in CH2Cl2 and exhibits an unparalleled molar absorptivity of 3.91 × 105 cm-1 M-1 and high transparency to light at 400-900 nm. It also exhibited high resistance toward both photobleaching and symmetry breaking due to its unique structural rigidity. It is feasible for in vivo bioimaging and particularly suitable to couple with the shorter-wavelength analogues for high-contrast multiplexing. High-contrast dual-channel intraoperative imaging of the hepatobiliary system and three-channel in vivo imaging of the intestine, the stomach, and the vasculature were showcased. EC7 is a benchmark fluorochrome for facile biomedical exploitation of the SWIR region beyond 1200 nm.

Furan Donor for NIR-II Molecular Fluorophores with Enhanced Bioimaging Performance.

The second near-infrared (NIR-II, 1,000 to 1,700 nm) molecular fluorophores containing donor-acceptor-donor conjugated backbone have attracted substantial attention due to their outstanding advantages, such as stable emission and facilely tuned photophysical properties. However, it is still challenging for them to simultaneously achieve high brightness and red-shifted absorption and emission. Herein, furan is adopted as the D unit to construct NIR-II fluorophores, demonstrating red shift of absorption, enhanced absorption coefficient, and fluorescent quantum yield when compared with the generally used thiophene counterparts. The high brightness and desirable pharmacokinetics of the optimized fluorophore, IR-FFCHP, endows improved performance for angiography and tumor-targeting imaging. Furthermore, dual-NIR-II imaging of tumor and sentinel lymph nodes (LNs) has been achieved with IR-FFCHP and PbS/CdS quantum dots, enabling the in vivo imaging navigated LN surgery in tumor-bearing mice. This work demonstrates the potential of furan for constructing bright NIR-II fluorophores for biological imaging.

Highly Structured Water Networks in Microhydrated Dodecaborate Clusters.

We report a combined photoelectron spectroscopy and theoretical investigation of a series of size-selected hydrated closo-dodecaborate clusters B12X122-·nH2O (X = H, F, or I; n = 1-6). Distinct structural arrangements of water clusters from monomer to hexamer can be achieved by using different B12X122- bases, illustrating the evident solute specificity. Because B-H···H-O dihydrogen bonds are stronger than O···H-O hydrogen bonds in water, the added water molecules are arranged in a unified binding mode by forming highly structured water networks manipulated by B12H122-. As a comparison, the hydrated B12F122- clusters display similar water evolution for n values of 1 and 2 but different binding modes for larger clusters, while water networks in B12I122- share similarities with the free water clusters. This finding provides a consistent picture of the structural diversity of hydrogen bonding networks in microhydrated dodecaborates and a molecular-level understanding of microsolvation dynamics in aqueous borate chemistry.

Rapid and Highly Efficient Genetic Transformation and Application of Interleukin-17B Expressed in Duckweed as Mucosal Vaccine Adjuvant.

Molecular farming utilizes plants as a platform for producing recombinant biopharmaceuticals. Duckweed, the smallest and fastest growing aquatic plant, is a promising candidate for molecular farming. However, the efficiency of current transformation methods is generally not high in duckweed. Here, we developed a fast and efficient transformation procedure in Lemna minor ZH0403, requiring 7-8 weeks from screening calluses to transgenic plants with a stable transformation efficiency of 88% at the DNA level and 86% at the protein level. We then used this transformation system to produce chicken interleukin-17B (chIL-17B). The plant-produced chIL-17B activated the NF-κB pathway, JAK-STAT pathway, and their downstream cytokines in DF-1 cells. Furthermore, we administrated chIL-17B transgenic duckweed orally as an immunoadjuvant with mucosal vaccine against infectious bronchitis virus (IBV) in chickens. Both IBV-specific antibody titer and the concentration of secretory immunoglobulin A (sIgA) were significantly higher in the group fed with chIL-17B transgenic plant. This indicates that the duckweed-produced chIL-17B enhanced the humoral and mucosal immune responses. Moreover, chickens fed with chIL-17B transgenic plant demonstrated the lowest viral loads in different tissues among all groups. Our work suggests that cytokines are a promising adjuvant for mucosal vaccination through the oral route. Our work also demonstrates the potential of duckweed in molecular farming.

Local endocytosis of sucrose transporter 2 in duckweed reveals the role of sucrose transporter 2 in guard cells.

The local endocytosis of membrane proteins is critical for many physiological processes in plants, including the regulation of growth, development, nutrient absorption, and osmotic stress response. Much of our knowledge on the local endocytosis of plasma membrane (PM) protein only focuses on the polar growth of pollen tubes in plants and neuronal axon in animals. However, the role of local endocytosis of PM proteins in guard cells has not yet been researched. Here, we first cloned duckweed SUT2 (sucrose transporter 2) protein and then conducted subcellular and histological localization of the protein. Our results indicated that LpSUT2 (Landoltia punctata 0202 SUT2) is a PM protein highly expressed on guard cells. In vitro experiments on WT (wild type) lines treated with high sucrose concentration showed that the content of ROS (reactive oxygen species) in guard cells increased and stomatal conductance decreased. We observed the same results in the lines after overexpression of the LpSUT2 gene with newfound local endocytosis of LpSUT2. The local endocytosis mainly showed that LpSUT2 was uniformly distributed on the PM of guard cells in the early stage of development, and was only distributed in the endomembrane of guard cells in the mature stage. Therefore, we found the phenomenon of guard cell LpSUT2 local endocytosis through the changes of duckweed stomata and concluded that LpSUT2 local endocytosis might be dependent on ROS accumulation in the development of duckweed guard cells. This paper might provide future references for the genetic improvement and water-use efficiency in other crops.

Effects of Heterogeneous Protein Environment on Excitation Energy Transfer Dynamics in the Fenna-Matthews-Olson Complex.

The Fenna-Matthews-Olson (FMO) complex of green sulfur bacteria has been serving as a prototypical light-harvesting protein for studying excitation energy transfer (EET) dynamics in photosynthesis. The most widely used Frenkel exciton model for FMO complex assumes that each excited bacteriochlorophyll site couples to an identical and isolated harmonic bath, which does not account for the heterogeneous local protein environment. To better describe the realistic environment, we propose to use the recently developed multistate harmonic (MSH) model, which contains a globally shared bath that couples to the different pigment sites according to the atomistic quantum mechanics/molecular mechanics simulations with explicit protein scaffold and solvent. In this work, the effects of heterogeneous protein environment on EET in FMO complexes from Prosthecochloris aestuarii and Chlorobium tepidum, specifically including realistic spectral density, site-dependent reorganization energies, and system-bath couplings are investigated. Semiclassical and mixed quantum-classical mapping dynamics were applied to obtain the nonadiabatic EET dynamics in several models ranging from the Frenkel exciton model to the MSH model and their variants. The MSH model with realistic spectral density and site-dependent system-bath couplings displays slower EET dynamics than the Frenkel exciton model. Our comparative study shows that larger average reorganization energy, heterogeneity in spectral densities, and low-frequency modes could facilitate energy dissipation, which is insensitive to the static disorder in reorganization energies. The effects of the spectral densities and system-bath couplings along with the MSH model can be used to optimize EET dynamics for artificial light-harvesting systems.

Annihilating Actinic Photochemistry of the Pyruvate Anion by One and Two Water Molecules.

Photochemical behaviors of pyruvic acid in multiple phases have been extensively studied, while those of its conjugate base, the pyruvate anion (CH3COCOO-, PA-) are less understood and remain contradictory in gaseous versus aqueous phases. Here in this article, we report a joint experimental and theoretical study combining cryogenic, wavelength-resolved negative ion photoelectron spectroscopy (NIPES) and high-level quantum chemical computations to investigate PA- actinic photochemistry and its dependence on microsolvation in the gas phase. PA-·nH2O (n = 0-5) clusters were generated and characterized, with their low-lying isomers identified. NIPES conducted at multiple wavelengths across the PA- actinic regime revealed the PA- photochemistry extremely sensitive to its hydration extent. While bare PA- anions exhibit active photoinduced dissociations that generate the acetyl (CH3CO-), methide (CH3-) anions, their corresponding radicals, and slow electrons, one single attached water molecule results in significant suppression with a subsequent second water being able to completely block all dissociation pathways, effectively annihilating all PA- photochemical reactivities. The underlying dissociation mechanisms of PA-·nH2O (n = 0-2) clusters are proposed involving nπ* excitation, dehydration, decarboxylation, and further CO loss. Since the photoexcited dihydrate does not have sufficient energy to overcome the full dehydration barrier before PA- could fragmentate, the PA- dissociation pathway is completely blocked, with the energy most likely released via loss of one water and internal electronic and vibrational relaxations. The insight unraveled in this work provides a much-needed critical link to connect the seemingly conflicting PA- actinic chemistry between the gas and condensed phases.

All-Atom Nonadiabatic Semiclassical Mapping Dynamics for Photoinduced Charge Transfer of Organic Photovoltaic Molecules in Explicit Solvents.

Direct all-atom simulation of nonadiabatic dynamics in disordered condensed phases like liquid solutions and amorphous solids has been challenging. The first all-atom simulation of the photoinduced charge-transfer dynamics of a prototypical organic photovoltaic carotenoid-porphyrin-C60 molecular triad in explicit tetrahydrofuran is presented. Based on the Meyer-Miller mapping Hamiltonian, various semiclassical and mixed quantum-classical dynamics are employed, including the linearized semiclassical, symmetrical quasiclassical, mean-field Ehrenfest, classical mapping model, and spin-mapping model approaches. The all-atom nonadiabatic dynamics were compared to multi-state harmonic models with a globally shared bath, and the models built using the ensemble averages on the initial electronic state could reproduce the all-atom results. The solvent effect was found to be critical for the photoinduced charge transfer, and the time-dependent solute-solvent radial distribution functions revealed that only the nonadiabatic dynamics started with the effective forces on the initial electronic state could capture the correct nuclear dynamics. The proposed strategy for modeling condensed-phase nonadiabatic dynamics with atomistic details is readily applied to complex condensed-phase systems.

Unraveling hydridic-to-protonic dihydrogen bond predominance in monohydrated dodecaborate clusters.

Hydridic-to-protonic dihydrogen bonds (DHBs) are involved in comprehensive structural and energetic evolution, and significantly affect reactivity and selectivity in solution and solid states. Grand challenges exist in understanding DHBs' bonding nature and strength, and how to harness DHBs. Herein we launched a combined photoelectron spectroscopy and multiscale theoretical investigation using monohydrated closo-dodecaborate clusters B12X12 2-·H2O (X = H, F, I) to address such challenges. For the first time, a consistent and unambiguous picture is unraveled demonstrating that B-H⋯H-O DHBs are superior to the conventional B-X⋯H-O HBs, being 1.15 and 4.61 kcal mol-1 stronger than those with X = F and I, respectively. Energy decomposition analyses reveal that induction and dispersion terms make pronounced contributions resulting in a stronger B-H⋯H-O DHB. These findings call out more attention to the prominent roles of DHBs in water environments and pave the way for efficient and eco-friendly catalytic dihydrogen production based on optimized hydridic-to-protonic interactions.

Super-stable cyanine@albumin fluorophore for enhanced NIR-II bioimaging.

Near-infrared-II (NIR-II) dyes could be encapsulated by either exogenous or endogenous albumin to form stable complexes for deep tissue bioimaging. However, we still lack a complete understanding of the interaction mechanism of the dye@albumin complex. Studying this principle is essential to guide efficient dye synthesis and develop NIR-II probes with improved brightness, photostability, etc. Methods: Here, we screen and test the optical and chemical properties of dye@albumin fluorophores, and systematically investigate the binding sites and the relationship between dye structures and binding degree. Super-stable cyanine dye@albumin fluorophores are rationally obtained, and we also evaluate their pharmacokinetics and long-lasting NIR-II imaging abilities. Results: We identify several key parameters of cyanine dyes governing the supramolecular/covalent binding to albumin, including a six-membered ring with chlorine (Cl), the small size of side groups, and relatively high hydrophobicity. The tailored fluorophore (IR-780@albumin) exhibits much-improved photostability, serving as a long-lasting imaging probe for NIR-II bioimaging. Conclusion: Our study reveals that the chloride-containing cyanine dyes with the above-screened chemical structure (e.g. IR-780) could be lodged into albumin more efficiently, producing a much more stable fluorescent probe. Our finding partly solves the photobleaching issue of clinically-available cyanine dyes, enriching the probe library for NIR-II bioimaging and imaging-guided surgery.

Forecasting nonadiabatic dynamics using hybrid convolutional neural network/long short-term memory network.

Modeling nonadiabatic dynamics in complex molecular or condensed-phase systems has been challenging, especially for the long-time dynamics. In this work, we propose a time series machine learning scheme based on the hybrid convolutional neural network/long short-term memory (CNN-LSTM) framework for predicting the long-time quantum behavior, given only the short-time dynamics. This scheme takes advantage of both the powerful local feature extraction ability of CNN and the long-term global sequential pattern recognition ability of LSTM. With feature fusion of individually trained CNN-LSTM models for the quantum population and coherence dynamics, the proposed scheme is shown to have high accuracy and robustness in predicting the linearized semiclassical and symmetrical quasiclassical mapping dynamics as well as the mixed quantum-classical Liouville dynamics of various spin-boson models with learning time up to 0.3 ps. Furthermore, if the hybrid network has learned the dynamics of a system, this knowledge is transferable that could significantly enhance the accuracy in predicting the dynamics of a similar system. The hybrid CNN-LSTM network is thus believed to have high predictive power in forecasting the nonadiabatic dynamics in realistic charge and energy transfer processes in photoinduced energy conversion.

Multi-state harmonic models with globally shared bath for nonadiabatic dynamics in the condensed phase.

Model Hamiltonians constructed from quantum chemistry calculations and molecular dynamics simulations are widely used for simulating nonadiabatic dynamics in the condensed phase. The most popular two-state spin-boson model could be built by mapping the all-atom anharmonic Hamiltonian onto a two-level system bilinearly coupled to a harmonic bath using the energy gap time correlation function. However, for more than two states, there lacks a general strategy to construct multi-state harmonic (MSH) models since the energy gaps between different pairs of electronic states are not entirely independent and need to be considered consistently. In this paper, we extend the previously proposed approach for building three-state harmonic models for photoinduced charge transfer to the arbitrary number of electronic states with a globally shared bath and the system-bath couplings are scaled differently according to the reorganization energies between each pair of states. We demonstrate the MSH model construction for an organic photovoltaic carotenoid-porphyrin-C60 molecular triad dissolved in explicit tetrahydrofuran solvent. Nonadiabatic dynamics was simulated using mixed quantum-classical techniques, including the linearized semiclassical and symmetrical quasiclassical dynamics with the mapping Hamiltonians, mean-field Ehrenfest, and mixed quantum-classical Liouville dynamics in two-state, three-state, and four-state harmonic models of the triad system. The MSH models are shown to provide a general and flexible framework for simulating nonadiabatic dynamics in complex systems.

Structural Reconstruction of Optically Invisible State in a Single Molecule via Scanning Tunneling Microscope.

Molecular dark states, participating in various energy- and electron-transfer processes, are typically beyond direct optical-spectroscopic measurements because of the forbidden transition dictated by the selection rule. In this work, we demonstrate a direct profile of the dark-state transition density of a single molecule on the subnanometer scale by using a scanning tunneling microscope. Our method allows one to resolve the four-lobe configuration in a 1 nm region for the example molecule. The current proposal will bring about a new methodology to study the single-molecule properties in electro-optical devices and light-assisted biological processes.