Large Energy Barrier Research Articles

Nonequilibrium statistical mechanics of money/energy exchange models

Many-body dynamical models in which Boltzmann statistics can be derived directly from the underlying dynamical laws without invoking the fundamental postulates of statistical mechanics are scarce. Interestingly, one such model is found in econophysics and in chemistry classrooms: the money game, in which players exchange money randomly in a process that resembles elastic intermolecular collisions in a gas, giving rise to the Boltzmann distribution of money owned by each player. Although this model offers a pedagogical example that demonstrates the origins of Boltzmann statistics, such demonstrations usually rely on computer simulations. In fact, a proof of the exponential steady-state distribution in this model has only become available in recent years. Here, we study this random money/energy exchange model and its extensions using a simple mean-field-type approach that examines the properties of the one-dimensional random walk performed by one of its participants. We give a simple derivation of the Boltzmann steady-state distribution in this model. Breaking the time-reversal symmetry of the game by modifying its rules results in non-Boltzmann steady-state statistics. In particular, introducing ‘unfair’ exchange rules in which a poorer player is more likely to give money to a richer player than to receive money from that richer player, results in an analytically provable Pareto-type power-law distribution of the money in the limit where the number of players is infinite, with a finite fraction of players in the ‘ground state’ (i.e. with zero money). For a finite number of players, however, the game may give rise to a bimodal distribution of money and to bistable dynamics, in which a participant’s wealth jumps between poor and rich states. The latter corresponds to a scenario where the player accumulates nearly all the available money in the game. The time evolution of a player’s wealth in this case can be thought of as a ‘chemical reaction’, where a transition between ‘reactants’ (rich state) and ‘products’ (poor state) involves crossing a large free energy barrier. We thus analyze the trajectories generated from the game using ideas from the theory of transition paths and highlight non-Markovian effects in the barrier crossing dynamics.

A new In Situ Oxidized 2D Layered MnBi2Te4 Cathode for High-Performance Aqueous Zinc-Ion Battery.

Recently, aqueous zinc ion batteries (AZIBs) with the superior theoretical capacity, high safety, low prices, and environmental protection, have emerged as a contender for advanced energy storage. However, challenges related to cathode materials, such as dissolution, instability, and structural collapse, have hindered the progress of AZIBs. Here, a novel AZIB is constructed using an oxidized 2D layered MnBi2Te4 cathode for the first time. The oxidized MnBi2Te4 cathode with large interlayer spacing and low energy barrier for zinc ion diffusion at 240°C, exhibited impressive characteristics, including a high reversibility capacity of 393.1mAhg-1 (0.4Ag-1), outstanding rate performance, and long cycle stability. Moreover, the corresponding aqueous button cell also exhibits excellent electrochemical performance. To demonstrate the application in practice in the realm of flexible wearable electronics, a quasi-solid-state micro ZIB (MZIB) is constructed and shows excellent flexibility and high-temperature stability (the capacity does not significantly degrade when the temperature reaches 100°C and the bending angle exceeds 150°). This research offers effective tactics for creating high-performance cathode materials for AZIBs.

Controllable spatial distribution of La dopants in perovskite NaTaO3 enhancing its photocatalytic performance of formaldehyde solution degradation and simultaneous hydrogen evolution

Photocatalytic degradation of aqueous organic pollutant while hydrogen evolution has become an attractive and potential approach to address environmental pollution and energy shortages. The design of highly efficient photocatalyst and the mechanism study are the keys for this issue. For this purpose, a series of rare earth La doped perovskite NaTaO3 were prepared by an easy solid-phase synthesis method. La doping changed the morphology, structure and physicochemical properties of NaTaO3 crystal. More importantly, it also found that controllable La dopants formed a concentration gradient between the surface and bulk of NaTaO3 crystal, which would cause a gradient of energy band structure. Noteworthy, 0.5La/NaTaO3 was identified as the intermediate state with the La doping from A sites to B sites and from bulk to surface in NaTaO3 crystal. It possessed a large La concentration gradient, leading to the better photoelectrochemical properties and photocatalytic performance than any other xLa/NaTaO3 catalyst. For the photocatalytic reaction over 0.5La/NaTaO3, HCHO was partially mineralized and gradually converted to HCOOH due to the large energy barriers of the intermediate reaction steps, while H2 was produced stably in the five recycle runs. The active species of •O2−, •OH and h+ were detected by the control experiments with trapping agents, and •O2− was confirmed to be the dominant one in the photocatalytic reaction. On this basis, the possible mechanism was proposed to understand the photocatalytic system in depth.

Coordination Environment Engineering of Metal Centers in Coordination Polymers for Selective Carbon Dioxide Electroreduction toward Multicarbon Products.

Electrocatalytic carbon dioxide reduction reaction (CO2RR) toward value-added chemicals/fuels has offered a sustainable strategy to achieve a carbon-neutral energy cycle. However, it remains a great challenge to controllably and precisely regulate the coordination environment of active sites in catalysts for efficient generation of targeted products, especially the multicarbon (C2+) products. Herein we report the coordination environment engineering of metal centers in coordination polymers for efficient electroreduction of CO2 to C2+ products under neutral conditions. Significantly, the Cu coordination polymer with Cu-N2S2 coordination configuration (Cu-N-S) demonstrates superior Faradaic efficiencies of 61.2% and 82.2% for ethylene and C2+ products, respectively, compared to the selective formic acid generation on an analogous polymer with the Cu-I2S2 coordination mode (Cu-I-S). In situ studies reveal the balanced formation of atop and bridge *CO intermediates on Cu-N-S, promoting C-C coupling for C2+ production. Theoretical calculations suggest that coordination environment engineering can induce electronic modulations in Cu active sites, where the d-band center of Cu is upshifted in Cu-N-S with stronger selectivity to the C2+ products. Consequently, Cu-N-S displays a stronger reaction trend toward the generation of C2+ products, while Cu-I-S favors the formation of formic acid due to the suppression of C-C couplings for C2+ pathways with large energy barriers.

Excited state dynamics of P-H···H-B and P-H···H-Si hydride-hydride interactions and potential dehydrogenation reactions in frustrated lewis pair

Dihydrogen interactions plays a crucial role in frustrated Lewis pairs (FLPs) strategy and promotes dehydrogenation reactions due to its low directionality and saturability. This work focuses on the excited-state dynamics of the P-H···H-B and P-H···H-Si intramolecular hydride-hydride interactions in 4-bis(pentafluorophenyl)-borane-5-dimesitylphosphino-9,9-dimethylxanthine (FPB-MP-MX) and 5-dimethylsilyl-9,9-dimethylxanthene-4-yl-diphenylphosphonium cation (MSi-PP-MX), respectively. The interaction between B-H, C-H and π electron of benzene ring are also considered. Upon photoexcitation to the first singlet (S1) state, the P-H···H-B of FPB-MP-MX and the P-H···H-Si of MSi-PP-MX are both strengthened, while B-H···π and C−H···π interaction are all weakened. These changes are induced by the charge transfer from the 9,9-dimethyl-xanthene moiety to the electron-deficient phosphorus cation and mesitylene group, which are demonstrated by the molecule orbital, electron–hole, and charge analysis. In addition, the potential energy curve of FPB-MP-MX scanned the P-H···H-B shows low energy barriers of 20.68 kcal mol−1 in the S0 state, implying the potential dehydrogenation reaction with lower energy of hydrogen product. In contrast to FPB-MP-MX, the potential energy curve of MSi-PP-MX scanned the P-H···H-Si has large energy barrier of 42.66 kcal mol−1 in the S0 state and 32.01 kcal mol−1 in the S1 state, which demonstrates the difficulty of dehydrogenation reaction. This works presents reasonable interpretation on the dynamics changes of dihydrogen bonding and dehydrogenation reaction of frustrated Lewis pairs upon photoexcitation.

Ligand Lipophilicity Determines Molecular Mechanisms of Nanoparticle Adsorption to Lipid Bilayers.

The interactions of ligand-functionalized nanoparticles with the cell membrane affect cellular uptake, cytotoxicity, and related behaviors, but relating these interactions to ligand properties remains challenging. In this work, we perform coarse-grained molecular dynamics simulations to study how the adsorption of ligand-functionalized cationic gold nanoparticles (NPs) to a single-component lipid bilayer (as a model cell membrane) is influenced by ligand end group lipophilicity. A set of 2 nm diameter NPs, each coated with a monolayer of organic ligands that differ only in their end groups, was simulated to mimic NPs recently studied experimentally. Metadynamics calculations were performed to determine key features of the free energy landscape for adsorption as a function of the distance of the NP from the bilayer and the number of NP-lipid contacts. These simulations revealed that NP adsorption is thermodynamically favorable for all NPs due to the extraction of lipids from the bilayer and into the NP monolayer. To resolve ligand-dependent differences in adsorption behavior, string method calculations were performed to compute minimum free energy pathways for adsorption. These calculations revealed a surprising nonmonotonic dependence of the free energy barrier for adsorption on ligand end group lipophilicity. Large free energy barriers are predicted for the least lipophilic end groups because favorable NP-lipid contacts are initiated only through the unfavorable protrusion of lipid tail groups out of the bilayer. The smallest free energy barriers are predicted for end groups of intermediate lipophilicity which promote NP-lipid contacts by intercalating within the bilayer. Unexpectedly, large free energy barriers are also predicted for the most lipophilic end groups which remain sequestered within the ligand monolayer rather than intercalating within the bilayer. These trends are broadly in agreement with past experimental measurements and reveal how subtle variations in ligand lipophilicity dictate adsorption mechanisms and associated kinetics by influencing the interplay of lipid-ligand interactions.

Alcohol‐Soluble n‐Type Polythiophenes as Cathode Interlayer in Organic Photodetectors for Hole Blocking

AbstractFor organic photodetectors (OPDs), cathode interlayer (CIL) with low‐lying highest occupied molecular orbital (EHOMO) energy level is required to reduce dark current density (Jd). In this study, toward application as CIL in OPDs, an alcohol‐processable n‐type conjugated polymer (n‐PT8) based on imide/cyano‐substituted polythiophene backbone and branched oligo(ethylene glycol) side chain is developed. Owing to the electron‐accepting imide/cyano groups on the backbone, n‐PT8 exhibits deep‐lying EHOMO of −5.80 eV and a high conductivity of 5.12 × 10−6 S cm−1. OPD with n‐PT8 as CIL exhibits dark current density one order of magnitude lower than that with the state‐of‐the‐art CIL material because of the large energy barrier for reverse hole injection. Moreover, the device performance is insensitive to the n‐PT8 layer thickness, which is very desirable for the mass production of OPDs. The near‐infrared (NIR) OPDs based on n‐PT8 exhibit an ultra‐low dark current density of 1.76 × 10−9 A cm−2 and a specific detectivity of 2.88 × 1012 cm Hz1/2 W−1 at −1 V. To the best knowledge, this is the first report on n‐type polythiophene derivatives as CIL in organic opto‐electronic devices.

Strain Effect on the Structural and Electronic Properties of a Monolayer C4N4

Abstract The first-principles calculations have been performed to examine structural, mechanical, and electronic properties at large stain for a monolayer C4N4, which was predicted as an anchoring promising material to attenuate shuttle effect in Li–S batteries stemming from its large absorption energy and low diffusion energy barrier. Our results show that the ideal strengths for C4N4 under tensile and pure shear deformation conditions reach 13.9 and 12.5 GPa at strain of 0.07 and 0.28, respectively. The folded five-membered rings and diverse bonding modes between carbon and nitrogen atoms enhances the ability to resist plastic deformation of C4N4. The orderly bond-rearranging behaviors under the weak tensile loading path along the [100] direction cause the impressive semiconductor-metal and inverse semiconductor-metal transition. The present results enrich the knowledge of the structure and electronic properties of C4N4 under deformations and shed light on exploring other two-dimensional materials under diverse loading conditions.

What a difference a chlorine makes: The remarkable unimolecular ion chemistry of phenyl formate and phenyl chloroformate.

Imaging photoelectron photoion coincidence (iPEPICO) spectroscopy and tandem mass spectrometry were employed to explore the ionisation and dissociative ionisation of phenyl formate (PF) and phenyl chloroformate (PCF). The threshold photoelectron spectra of both compounds are featureless and lack a definitive origin transition, owing to the internal rotation of the formate functional group relative to the benzene ring, active upon ionisation. CBS-QB3 calculations yield ionisation energies of 8.88 and 9.03 eV for PF and PCF, respectively. Ionised PF dissociates by the loss of CO via a transition state composed of a phenoxy cation and HCO moieties. The dissociation of PCF ions involves the competing losses of CO (m/z 128/130), Cl (m/z 121) and CO2 (m/z 112/114), with Cl loss also shown to occur from the second excited state in a non-statistical process. The primary CO- and Cl-loss fragment ions undergo sequential reactions leading to fragment ions at m/z 98 and 77. The mass-analysed ion kinetic energy (MIKE) spectrum of PCF+ showed that the loss of CO2 occurs with a large reverse energy barrier, which is consistent with the computationally derived minimum energy reaction pathway.

The local variation of the Gaussian modulus enables different pathways for fluid lipid vesicle fusion

Viral infections, fertilization, neurotransmission, and many other fundamental biological processes rely on membrane fusion. Straightforward calculations based on the celebrated Canham–Helfrich elastic model predict a large topological energy barrier that prevents the fusion process from being thermally activated. While such high energy is in accordance with the physical barrier function of lipid membranes, it is difficult to reconcile with the biological mechanisms involved in fusion processes. In this work, we use a Ginzburg–Landau type of free energy that recovers the Canham–Helfrich model in the limit of small width-to-vesicle-extension ratio, with the additional ability to handle topological transitions. We show that a local modification of the Gaussian modulus in the merging region both dramatically lowers the elastic energy barrier and substantially changes the minimal energy pathway for fusion, in accordance with experimental evidence. Therefore, we discuss biological examples in which such a modification might play a crucial role.

Insights into the roles of superficial lattice oxygen in formaldehyde oxidation on birnessite.

K+-modified birnessite materials were constructed to remove formaldehyde (HCHO) in this work. The introduction of K+ led to weakening of the Mn-O bonds and enhanced the migration of superficial lattice oxygen, resulting in improved redox properties and catalytic activity. MnO2-3K with the largest specific surface area and greatest abundance of superficial lattice oxygen showed the best catalytic performance at 30-130 °C. The operando analyses reveal that HCHO is primarily activated to dioxymethylene (DOM) and subsequently converted to formate species (*COOH). The accumulation of formate species caused a decline in catalytic performance during extended testing at 30 °C, a challenge that could be mitigated by raising the temperature. Theoretical studies disclose that the *COOH → *H2CO3 step with the largest energy barrier is the rate limiting step for HCHO deep decomposition. Molecular oxygen could be activated at oxygen vacancies to replenish the depleted lattice oxygen after decomposition of carbonate species (*H2CO3) and CO2 and H2O desorption. The adsorbed oxygen and water did not limit the deep oxidation of HCHO. This research presents a promising approach for designing highly efficient, non-noble metal catalysts for formaldehyde degradation.

Mechanistic studies of HF/BF3-catalyzed anthracene polymerization to prepare mesophase pitch.

The mesophase pitch prepared by acid catalytic method typically had the advantages of low softening point and high solubility. To fully understand the mechanism of acid-catalyzed reactions and gain a deeper understanding of the microstructure of mesophase pitch, this article studied the mechanism of hydrofluoride/boron trifluoride (HF/BF3)-catalyzed anthracene using molecular simulation methods. The results showed that there might be two types of carbocations present in the system: classical and non-classical carbocations, and five reactions might occur, protonation reaction, chain elongation reaction, intramolecular cyclization reaction, deprotonation reaction, and dehydrogenation reaction. Classical carbocations acted as reactive intermediates in the chain elongation reaction and intramolecular cyclization reaction. When anthracene occurred chain elongation reactions with carbocations to form polymers, the generation of the tetramer required lager energy barriers than that of the dimer and trimer. The stiffness and flatness of molecules could be increased via intramolecular cyclization reactions. The polymers of anthracene might also occurred dehydrogenation reactions when the non-classical carbocations played the role of reactive intermediates. The dehydrogenation reactions required large energy barriers, which might be the reason for the product having a high aliphatic hydrogen content. The Materials Studio (MS) 2020 software was used to complete the simulation. The atomic charge distribution calculation and the structure optimization of molecules were carried out using the B3LYP functional and DNP basis. The DFT-D (TS) dispersion corrections were added to calculate the dispersion interaction between aromatic molecules. The complete LST/QST method was used to search the transition states and calculate the reaction energy barrier.

Passivating Dipole Layer Bridged 3D/2D Perovskite Heterojunction for Highly Efficient and Stable p-i-n Solar Cells.

Constructing 3D/2D perovskite heterojunction is a promising approach to integrate the benefits of high efficiency and superior stability in perovskite solar cells (PSCs). However, in contrast to n-i-p architectural PSCs, the p-i-n PSCs with 3D/2D heterojunction have serious limitations in achieving high-performance as they suffer from a large energetic mismatch and electron extraction energy barrier from a 3D perovskite layer to a 2D perovskite layer, and serious nonradiative recombination at the heterojunction. Here a strategy of incorporating a thin passivating dipole layer (PDL) onto 3D perovskite and then depositing 2D perovskite without dissolving the underlying layer to form an efficient 3D/PDL/2D heterojunction is developed. It is revealed that PDL regulates the energy level alignment with the appearance of interfacial dipole and strongly interacts with 3D perovskite through covalent bonds, which eliminate the energetic mismatch, reduce the surface defects, suppress the nonradiative recombination, and thus accelerate the charge extraction at such electron-selective contact. As a result, it is reported that the 3D/PDL/2D junction p-i-n PSCs present a power conversion efficiency of 24.85% with robust stability, which is comparable to the state-of-the-art efficiency of the 3D/2D junction n-i-p devices.

Red Fluorescent Carbon Dots with Alkyl Chain Achieving Stable Electroluminescence via an In Situ Electric Excitation

AbstractThe energy barrier between the highest occupied molecular orbital (HOMO) of the emission layer (EML) and the hole transport layer material (HTL) restricts the development of carbon dots (CDs) based light‐emitting diodes (LEDs). Here, the fabrication of red fluorescent CDs (RCDs) by a one‐step solvothermal method is reported. These RCDs have a photoluminescence quantum yield (PLQY) of 47.97% and a full width at half maximum (FWHM) of 26 nm. This study also shows the RCDs‐based LEDs fabrication with Poly(9,9‐dioctylfluorene‐co‐N‐(4‐butylphenyl) diphenylamine (TFB) as HTL. In normal case, these devices are not able to work due to the large interfacial energy barrier between RCDs and TFB. While, the RCDs‐LEDs can overcome through interfacial energy barriers and achieve stable carrier injecting by a simple in situ electric excitation at the current of 50 mA cm−2. This work provides a new strategy to overcome the obstacle of mismatch of interfacial energy levels in the LEDs by an in situ electric excitation.

Microscopic insights on ion transport in Li3OCl1−xBrx anti-perovskites from metadynamics simulations

The recently discovered anti-perovskites of the formula, Li3OCl1−xBrx, where x=0 to 1, have been garnering interest as potential candidates for solid electrolytes in battery applications. It is observed that the Li ion transport in these solids is rather slow, and unaccessible within typical molecular dynamics time scales. However, by judicially augmenting it with the accelerated sampling technique of metadynamics, the present study derives fresh insights on the nature of Li ion transport in these systems. The microscopic of ion migration along intra- and inter-octahedral channels, suggests that intra-octahedral channels account for over 95% Li transport in the system. The bromide end member offers lower free energy barriers, due to entropic factors resulting from the expansion of the lattice. However, the large free energy barriers estimated in the present work suggest that the undoped Li3OCl1−xBrx anti-perovskites are unlikely to exhibit superionic behavior.

Tailoring Crystallization Dynamics of CsPbI3 for Scalable Production of Efficient Inorganic Perovskite Solar Cells

AbstractAll‐inorganic perovskite cesium lead triiodide (CsPbI3) with inorganic nature, low‐temperature synthesis, and a suitable bandgap is desirable for high‐performance photovoltaics. However, the scalable production of CsPbI3 photovoltaics is still challenging due to a large nucleation energy barrier and slow phase transition during unassisted natural crystallization. Here, the crystallization dynamics of CsPbI3 thin films is tailored via lead acetate (PbAc2) substitution in the perovskite precursor ink, allowing the scalable fabrication of efficient all‐inorganic perovskite solar cells and minimodules. Introducing PbAc2 enlarges CsPbI3 colloid size in the precursor and reduces the nucleation energy barrier. Additionally, reactions between acetate and dimethylammonium in the wet film accelerate the removal of dimethylammonium additives and generate solvent vapors for self‐regulate internal solvent annealing, resulting in densely packed, uniform, and pinhole‐free CsPbI3 perovskite films over large areas. This strategy demonstrates inverted CsPbI3 solar cells with 20.17% efficiency and good operational stability (retaining 95.5% of initial efficiency after continuous operation for 1800 h) and 15.1%‐efficient CsPbI3 minimodules with an active area of 26.8 cm2.

Enthalpy-entropy compensation in the slow Arrhenius process.

The Meyer-Neldel compensation law, observed in a wide variety of chemical reactions and other thermally activated processes, provides a proportionality between the entropic and the enthalpic components of an energy barrier. By analyzing 31 different polymer systems, we show that such an intriguing behavior is encountered also in the slow Arrhenius process, a recently discovered microscopic relaxation mode, responsible for several equilibration mechanisms both in the liquid and the glassy state. We interpret this behavior in terms of the multiexcitation entropy model, indicating that overcoming large energy barriers can require a high number of low-energy local excitations, providing a multiphonon relaxation process.

A 2D Ba2N Electride for Transition Metal-Free N2 Dissociation under Mild Conditions.

N2 activation is a key step in the industrial synthesis of ammonia and other high-value-added N-containing chemicals, and typically is heavily reliant on transition metal (TM) sites as active centers to reduce the large activation energy barrier for N2 dissociation. In the present work, we report that a 2D electride of Ba2N with anionic electrons in the interlayer spacings works efficiently for TM-free N2 dissociation under mild conditions. The interlayer electrons significantly boost N2 dissociation with a very small activation energy of 35 kJ mol-1, as confirmed by the N2 isotopic exchange reaction. The reaction of anionic electrons with N2 molecules stabilizes (N2)2- anions, the so-called diazenide, in the large interlayer space (∼4.5 Å) sandwiched by 2 cationic slabs of Ba2N as the main intermediate.

Facet-dependent catalytic activity of shape-controllable palladium nanocrystals with clean surface in acetophenone selective hydrogenation

Shape-controlled metal nanocrystals have wide applications in catalysis. However, the capping agents playing significant roles in the shape-controlled synthesis often remain on the nanocrystal surfaces and are difficult to be removed completely, which not only causes the decrease in activity but also hinders the establishement of the correlation between various facets and intrinsic activity. In our present work, surface-clean Pd nanocrystals enclosed by different facets without capping agents were successfully synthesized by simply tuning the reduction kinetics in ascorbic acid mediated reduction of H2PdCl4 in water system. It was found that the turnover frequency (TOF) in acetophenone selective hydrogenation decreased with the decrease of the percentage of Pd{100} facet exposed in the Pd nanocrystals. The TOF value on Pd{100} facet was found 10 times higher than that on Pd{111} facet, while Pd{110} facet was found not favorable for acetophenone hydrogenation. Density functional theory (DFT) calculations reveal the more negative adsorption energy of acetophenone, the relatively shorter OPd distance between carbonyl group and the Pd surface, along with the much lower energy barrier in the acetophenone hydrogenation reaction, which leads to the Pd{100} surface exhibiting much higher TOF value than the other two surfaces. As for the Pd{110} surface, the long OPd distance, together with the large energy barrier makes it not favorable for the acetophenone hydrogenation.

Understanding the Multifaceted Mechanism of Compound I Formation in Unspecific Peroxygenases through Multiscale Simulations.

Unspecific peroxygenases (UPOs) can selectively oxyfunctionalize unactivated hydrocarbons by using peroxides under mild conditions. They circumvent the oxygen dilemma faced by cytochrome P450s and exhibit greater stability than the latter. As such, they hold great potential for industrial applications. A thorough understanding of their catalysis is needed to improve their catalytic performance. However, it remains elusive how UPOs effectively convert peroxide to Compound I (CpdI), the principal oxidizing intermediate in the catalytic cycle. Previous computational studies of this process primarily focused on heme peroxidases and P450s, which have significant differences in the active site from UPOs. Additionally, the roles of peroxide unbinding in the kinetics of CpdI formation, which is essential for interpreting existing experiments, have been understudied. Moreover, there has been a lack of free energy characterizations with explicit sampling of protein and hydration dynamics, which is critical for understanding the thermodynamics of the proton transport (PT) events involved in CpdI formation. To bridge these gaps, we employed multiscale simulations to comprehensively characterize the CpdI formation in wild-type UPO from Agrocybe aegerita (AaeUPO). Extensive free energy and potential energy calculations were performed in a quantum mechanics/molecular mechanics setting. Our results indicate that substrate-binding dehydrates the active site, impeding the PT from H2O2 to a nearby catalytic base (Glu196). Furthermore, the PT is coupled with considerable hydrogen bond network rearrangements near the active site, facilitating subsequent O-O bond cleavage. Finally, large unbinding free energy barriers kinetically stabilize H2O2 at the active site. These findings reveal a delicate balance among PT, hydration dynamics, hydrogen bond rearrangement, and cosubstrate unbinding, which collectively enable efficient CpdI formation. Our simulation results are consistent with kinetic measurements and offer new insights into the CpdI formation mechanism at atomic-level details, which can potentially aid the design of next-generation biocatalysts for sustainable chemical transformations of feedstocks.