Intramolecular boron-locking strategy induced remarkable first hyperpolarizability: role of torsion angles between donor and acceptor units.

In conventional strategies to design donor-acceptor (D-A) organic molecules with a large electronic contribution to the first hyperpolarizability (ß), the effects of the torsion angles (θ1 and θ2) between donor and acceptor moieties are barely considered. To address this issue, in this work, a promising and novel intramolecular boron-locking strategy combined with the different locking groups of different acceptors to control θ1 and θ2, has been proposed to make D-A organic molecules with large ß values. Intriguingly, reducing the torsion angles will make the ß value of the pyridiny thiophene triphenylamine unit (Py-Th-TPA) dramatically increase up to 94%, which is mainly ascribed to the smaller θ1 and θ2 leading to lower excited energy of the crucial excited state, and enhanced charge transfer (CT) from TPA to Py-Th moieties, and finally greatly increase the donor and acceptor part contributions to ß. Correlation between the difference, |θ1 - θ2| and ß, provides a large coefficient of determination, R2 = 0.78, which demonstrates that |θ1 - θ2| can be regarded as a potential descriptor for designing nonlinear optics (NLO) materials with D-A architecture. Clearly, we uncovered that θ1 and θ2 play a crucial role in the performance of NLO materials with D-A fragments.

The development of the QM/MM interface and its application for the on-the-fly QM/MM nonadiabatic dynamics in JADE package: Theory, implementation, and applications.

Understanding the nonadiabatic dynamics of complex systems is a challenging task in computational photochemistry. Herein, we present an efficient and user-friendly quantum mechanics/molecular mechanics (QM/MM) interface to run on-the-fly nonadiabatic dynamics. Currently, this interface consists of an independent set of codes designed for general-purpose use. Herein, we demonstrate the ability and feasibility of the QM/MM interface by integrating it with our long-term developed JADE package. Tailored to handle nonadiabatic processes in various complex systems, especially condensed phases and protein environments, we delve into the theories, implementations, and applications of on-the-fly QM/MM nonadiabatic dynamics. The QM/MM approach is established within the framework of the additive QM/MM scheme, employing electrostatic embedding, link-atom inclusion, and charge-redistribution schemes to treat the QM/MM boundary. Trajectory surface-hopping dynamics are facilitated using the fewest switches algorithm, encompassing classical and quantum treatments for nuclear and electronic motions, respectively. Finally, we report simulations of nonadiabatic dynamics for two typical systems: azomethane in water and the retinal chromophore PSB3 in a protein environment. Our results not only illustrate the power of the QM/MM program but also reveal the important roles of environmental factors in nonadiabatic processes.

On-the-fly simulation of time-resolved fluorescence spectra and anisotropy.

We combine on-the-fly trajectory surface hopping simulations and the doorway-window representation of nonlinear optical response functions to create an efficient protocol for the evaluation of time- and frequency-resolved fluorescence (TFRF) spectra and anisotropies of the realistic polyatomic systems. This approach gives the effective description of the proper (e.g., experimental) pulse envelopes, laser field polarizations, and the proper orientational averaging of TFRF signals directly from the well-established on-the-fly nonadiabatic dynamic simulations without extra computational cost. To discuss the implementation details of the developed protocol, we chose cis-azobenzene as a prototype to simulate the time evolution of the TFRF spectra governed by its nonadiabatic dynamics. The results show that the TFRF is determined by the interplay of several key factors, i.e., decays of excited-state populations, evolution of the transition dipole moments along with the dynamic propagation, and scaling factor of the TFRF signals associated with the cube of emission frequency. This work not only provides an efficient and effective approach to simulate the TFRF and anisotropies of realistic polyatomic systems but also discusses the important relationship between the TFRF signals and the underlining nonadiabatic dynamics.

Torsion Angles between Donor and Acceptor Moieties as a Descriptor for Designing Nonlinear Optics and Thermally Activated Delayed Fluorescence Materials.

The performances of nonlinear optics (NLO) and thermally activated delayed fluorescence (TADF) materials are strongly related to the torsion angles (θ) between donor (D) and acceptor (A) moieties in D-A architecture molecules. However, the underlying relationships connecting θ to the performances of NLO/TADF materials remain unclear. Herein, we present a comprehensive theoretical study on NLO/TADF materials composed of a series of D-A backbone molecules (TPAAP/TPAAQ series and AQ-DMAC/AQ-MeFAC series) to shed light on these relationships. It is found that changing θ via the intramolecular locking strategy can greatly influence values of the first hyperpolarizability (ß) and singlet-triplet energy gap (ΔEST), further leading to better/worse performances of NLO/TADF materials, respectively. Intriguingly, a more detailed analysis indicates that the variation trends between θ and ß/ΔEST are changeable in low θ regions, exhibiting volcano-like relationships. The large coefficients of determination (R2, ranging from 0.76 to 0.93) suggest that this experimentally measurable parameter (θ) can be used as a promising descriptor to evaluate the performances of related materials. Following the revealed θ-ß/θ-ΔEST correlations, the optimal/worst torsion angles for different materials are identified. These findings highlight the importance of the intrinsic structure-performance relationships, thus providing novel design strategies for high-performance NLO/TADF materials.

The impact of different geometrical restrictions on the nonadiabatic photoisomerization of biliverdin chromophores.

The photoisomerization mechanism of the chromophore of bacterial biliverdin (BV) phytochromes is explored via nonadiabatic dynamics simulation by using the on-the-fly trajectory surface-hopping method at the semi-empirical OM2/MRCI level. Particularly, the current study focuses on the influence of geometrical constrains on the nonadiabatic photoisomerization dynamics of the BV chromophore. Here a rather simplified approach is employed in the nonadiabatic dynamics to capture the features of geometrical constrains, which adds mechanical restrictions to the specific moieties of the BV chromophore. This simplified method provides a rather quick approach to examine the influence of geometrical restrictions on photoisomerization. As expected, different constrains bring distinctive influences on the photoisomerization mechanism of the BV chromophore, giving either strong or minor modification of both involved reaction channels and excited-state lifetimes after the constrains are added in different ring moieties. These observations not only contribute to the primary understanding of the role of the spatial restriction caused by biological environments in photoinduced dynamics of the BV chromophore, but also provide useful ideas for the artificial regulation of the photoisomerization reaction channels of phytochrome proteins.

An intramolecular-locked strategy for designing nonlinear optical materials with remarkable first hyperpolarizability.

To meet the expanding demands of high performance nonlinear optical (NLO) materials, an unprecedented intramolecular-locked strategy is proposed to design NLO materials with remarkable static first hyperpolarizability (ß0). This strategy means that importing a large steric hindrance group diphenylmethane (DPM) decreases the torsion angles (θ) between the donor {triphenylamine (TPA)} and acceptor {9-H-thioxanthen-9-one-10,10-dioxide (TXO)} units, as well as between the donor (TPA) and π-bridge (benzene) fragments. The decrease of θ can accelerate the intramolecular charge transfer and enhance the contributions of the TPA, TXO and quinoxaline-6,7-dicarbo-nitrile (QCN) fragments to the axial component of the ß0 value, and then the ß0 values of TPA-TXO (ß0 = 10 762 au) and TPA-QCN (ß0 = 22 495 au) are increased by 14.9% and 34.4%, respectively. Overall, the intramolecular-locked strategy is very effective for designing high performance NLO materials.

Tuning the first hyperpolarizability of hexaphyrins with different connections of mislinked pyrrole units: a theoretical study.

In the satisfactory design and synthesis of high-performance nonlinear optical (NLO) materials, for meeting the rapidly expanding demands of optoelectronic devices, a deeper understanding of the relationship between the structures and NLO properties has become a key issue. Herein, five novel mislinked expanded hexaphyrins with different connections of pyrrole units are selected to study the relationship between the structures and NLO properties. These five mislinked expanded hexaphyrins are neo-fused, neo-confused hexaphyrins, singly, doubly, and triply N-confused hexaphyrins. From theoretical results, the order of the static first hyperpolarizability (ß0) values is found to be: neo-fused hexaphyrin (ß0 = 4163 a.u.) < neo-confused hexaphyrin (ß0 = 5494 a.u.) < singly N-confused hexaphyrin (ß0 = 6510 a.u.) < doubly N-confused hexaphyrin (ß0 = 15 130 a.u.) < triply N-confused hexaphyrin (ß0 = 26 095 a.u.). Furthermore, ß0 values of the doubly and triply N-confused hexaphyrins are improved 2.1 and 3.7 times over that of their usual parent hexaphyrin (ß0 = 7120 a.u.), respectively. It is worth noting that increasing mislinked connection numbers and changing mislinked connection ways of the pyrrole units in these mislinked expanded hexaphyrins plays a crucial role in the tune of their second-order NLO responses.

Nonadiabatic molecular dynamics simulation for the ultrafast photoisomerization of dMe-OMe-NAIP based on TDDFT on-the-fly potential energy surfaces.

Global switching on-the-fly trajectory surface hopping molecular dynamics simulation was performed on the accurate TD-B3LYP/6-31G* potential energy surfaces for E-to-Z and Z-to-E photoisomerization of dMe-OMe-NAIP up to S1(ππ*) excitation. The present TD(DFT) simulation provides accurate calculation for conical intersections between the first-excited and ground states. Thus, simulated quantum yield and lifetime of 0.23 and 620 fs (0.15 and 600 fs) for E-to-Z (Z-to-E) isomerization are in good (relatively good) agreement with experimental observation of 0.25 and 480 fs (0.24 and 430 fs), respectively. Simulated results reveal that photoisomerization pathways are initially uphill to conical intersection zones on the S1 potential energy surface and then downhill to product zones. Three types of representative conical intersections are found for determining photoisomerization mechanisms: one is the rotation type responsible for reactive isomerization and the other two are close to E and Z configurations, respectively, only for nonreactive isomerization. The present conclusions can be held in general for similar large NAIP systems of photoinduced isomerization based on E and Z configurations.

Photoisomerization-mechanism-associated excited-state hydrogen transfer in 2'-hydroxychalcone revealed by on-the-fly trajectory surface-hopping molecular dynamics simulation.

By performing global-switching on-the-fly trajectory surface-hopping molecular dynamics simulation at the OM2/MRCI (14,15) quantum level, we probed the S3(ππ*) photoisomerization mechanisms associated with excited-state intramolecular hydrogen transfer for 2'-hydroxychalcone (2HC) within the interwoven conical intersection networks from four singlet electronic states (S3, S2, S1, and S0). The simulated quantum yields of 0.03 for cis-to-trans and zero for trans-to-cis photoisomerization were due to almost all the conical intersections being localized either in the cis-2HC or in trans-2HC region, and there was little chance for sampling trajectories to reach the rotation conical intersection (S1/S0) in between cis-2HC and trans-2HC that is key for reactive isomerization. The potential energy well on the S1 state in the trans-2HC region prevents trajectories from trans-to-cis photoisomerization, while the fact there is no well on S1 state in cis-2HC region opens a few chances for trajectories to reach the rotation conical intersections. The present simulation found that excited-state intramolecular hydrogen transfers in 2HC have a negative impact for reactive isomerization, and that hydrogen transfers take place on the S1 state, while back-transfer on the S0 state prevents sampling trajectories reaching rotational conical intersections. It was realized that it could be possible to enhance the quantum yield of 2HC photoisomerization by suppressing the hydrogen transfer (such as by changing an electron-donating substitution or adjusting the substitution position to decrease the acidity of the phenol group). From a perspective view of the potential energy surfaces, the theoretical design of such 2HC derivatives could enhance (control) the quantum yield by shifting the conical intersections away from the cis- and trans-region.

Theoretical studies on triplet-state driven dissociation of formaldehyde by quasi-classical molecular dynamics simulation on machine-learning potential energy surface.

The H-atom dissociation of formaldehyde on the lowest triplet state (T1) is studied by quasi-classical molecular dynamic simulations on the high-dimensional machine-learning potential energy surface (PES) model. An atomic-energy based deep-learning neural network (NN) is used to represent the PES function, and the weighted atom-centered symmetry functions are employed as inputs of the NN model to satisfy the translational, rotational, and permutational symmetries, and to capture the geometry features of each atom and its individual chemical environment. Several standard technical tricks are used in the construction of NN-PES, which includes the application of clustering algorithm in the formation of the training dataset, the examination of the reliability of the NN-PES model by different fitted NN models, and the detection of the out-of-confidence region by the confidence interval of the training dataset. The accuracy of the full-dimensional NN-PES model is examined by two benchmark calculations with respect to ab initio data. Both the NN and electronic-structure calculations give a similar H-atom dissociation reaction pathway on the T1 state in the intrinsic reaction coordinate analysis. The small-scaled trial dynamics simulations based on NN-PES and ab initio PES give highly consistent results. After confirming the accuracy of the NN-PES, a large number of trajectories are calculated in the quasi-classical dynamics, which allows us to get a better understanding of the T1-driven H-atom dissociation dynamics efficiently. Particularly, the dynamics simulations from different initial conditions can be easily simulated with a rather low computational cost. The influence of the mode-specific vibrational excitations on the H-atom dissociation dynamics driven by the T1 state is explored. The results show that the vibrational excitations on symmetric C-H stretching, asymmetric C-H stretching, and C=O stretching motions always enhance the H-atom dissociation probability obviously.

Functional and Basis Set Dependence for Time-Dependent Density Functional Theory Trajectory Surface Hopping Molecular Dynamics: Cis-Azobenzene Photoisomerization.

Within three functionals (TD-B3LYP, TD-BHandHLYP, and TD-CAM-B3LYP) in combination with four basis sets (3-21g, 6-31g, 6-31g(d), and cc-pvdz), global switching (GS) trajectory surface hopping molecular dynamics has been performed for cis-to-trans azobenzene photoisomerization up to the S1 (nπ*) excitation. Although all the combinations show artificial double-cone structure of conical intersection between ground and first excited states, simulated quantum yields and lifetimes are in good agreement with one another; 0.6 (±5%) and 40.5 fs (±10%) by TD-B3LYP, 0.5 (±10%) and 35.5 fs (±4%) by TD-BHandHLYP, and 0.44 (±9%) and 35.2 fs (±10%) by TD-CAM-B3LYP. By analyzing distributions of excited-state population decays, hopping spots, and typical trajectories with performance of 12 functional/basis set combinations, it has been concluded that functional dependence for given basis set is slightly more sensitive than basis set dependence for given functional. The present GS on-the-fly time-dependent density functional theory (TDDFT) trajectory surface hopping simulation can provide practical benchmark guidelines for conical intersection driven excited-state molecular dynamics simulation involving in large complex system within ordinary TDDFT framework. © 2019 Wiley Periodicals, Inc.

Unraveling the enhancement mechanisms of H2S sensing on a SnO2 surface: an ab initio perspective.

Accurate and effective sensing of H2S is one of the most complex and challenging tasks. Recent studies have demonstrated that the development of an Sb-doped SnO2 nanoribbon sensor can enhance the detection limit of H2S. To clarify the enhancement mechanism, various factors that regulate the sensing processes, such as the Sb-doped sites, surface oxygen defects and possible pre-adsorbed oxygen species, are considered in this study. Theoretical calculations reveal a thorough and extensive understanding of the gas-sensing mechanisms. Once the H2S gas interacted with the Sb-doped SnO2(110) surface, the molecule released electrons back to the surface, together with a decreased resistance level and strengthened detection signal. In addition, the dissociative adsorption of the O2 molecule also plays a significant role in the sensing processes. It is expected that the present work can provide effective guidance for improving the sensitivity of metal oxide surfaces and shed new light on the development of next generation gas-sensing materials.

Insight into the Expanded Mislinked Porphyrins with High Second Order Nonlinear Optical Response.

Materials with outstanding nonlinear optical (NLO) response exhibit excellent prospects in electrooptic devices. Thus, it is essential to find a high-performance NLO material to meet the growing demand for high-speed data transmission. In this study, theoretical investigations on the second order NLO properties of the novel expanded mislinked thia-norhexaphyrin, sulfur-free pentaphyrin, and their substituted derivatives were performed using density functional theory. Theoretical calculations display that the approximate planar structures of sulfur-free pentaphyrin embedded with two five-membered rings exhibits a remarkable NLO response and holds large dipolar contribution (ΦJ=1 = 63.5%) to the first hyperpolarizability among four parent expanded mislinked porphyrins. The static first hyperpolarizability values of these expanded porphyrins were found to range from 3490 to 14 229 au. In addition, the second order NLO response of these porphyrins has greatly improved except for minority electron-releasing- and electron-withdrawing-group substituted cases, and the static first hyperpolarizability value has increased to 47 950 au after installing the donor and acceptor groups. Unambiguous evidence reveals that expanded mislinked porphyrin can serve as a potential candidate for NLO materials.

Boosting the Quantum Efficiency of Ultralong Organic Phosphorescence up to 52 % via Intramolecular Halogen Bonding.

Ultralong organic phosphorescence (UOP) has attracted increasing attention due to its potential applications in optoelectronics, bioelectronics, and security protection. However, achieving UOP with high quantum efficiency (QE) over 20 % is still full of challenges due to intersystem crossing (ISC) and fast non-radiative transitions in organic molecules. Here, we present a novel strategy to enhance the QE of UOP materials by modulating intramolecular halogen bonding via structural isomerism. The QE of CzS2Br reaches up to 52.10 %, which is the highest afterglow efficiency reported so far. The crucial reason for the extraordinary QE is intramolecular halogen bonding, which can not only effectively enhance ISC by promoting spin-orbit coupling, but also greatly confine motions of excited molecules to restrict non-radiative pathways. This work provides a reasonable strategy to develop highly efficient UOP materials for practical applications.

Theoretical study on the reaction mechanism of OH radical with Z(E)-CF3CH[double bond, length as m-dash]CHF.

Understanding the atmospheric fate of hydrofluoroolefins (HFOs) is of great significance to assess their potential risk to the environment. As an important type of HFO, the comprehensive transformation mechanism and kinetics of Z(E)-CF3CH[double bond, length as m-dash]CHF initiated by OH radicals were investigated by performing quantum chemical calculations at the CCSD(T)/aug-cc-pVTZ//MP2/cc-pVDZ level. The results show that the OH-addition pathways are the most favorable for the title reaction. The rate constants are obtained by transition state theory with Wigner tunneling correction (TST/W). The calculated total rate constants are in good agreement with the experimental data. At 298 K, the computed rate constant and lifetime of Z(E)-CF3CH[double bond, length as m-dash]CHF are 9.66 × 10-13 (4.02 × 10-13) cm3 molecule-1 s-1 and 12.3 (29.7) days, respectively, which demonstrates that Z(E)-CF3CH[double bond, length as m-dash]CHF is atmospherically persistent.

3D-Flower-Like Copper Sulfide Nanoflake-Decorated Carbon Nanofragments-Modified Glassy Carbon Electrodes for Simultaneous Electrocatalytic Sensing of Co-existing Hydroquinone and Catechol.

A copper sulfide nanoflakes-decorated carbon nanofragments-modified glassy carbon electrode (CuS-CNF/GCE) was fabricated for the electrocatalytic differentiation and determination of hydroquinone (HQ) and catechol (CC). The physicochemical properties of the CuS-CNF were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. The electrocatalytic determination of HQ and CC over the CuS-CNF/GCE was evaluated by cyclic voltammetry and differential pulse voltammetry. An excellent detection limit and sensitivity of the CuS-CNF/GCE are obtained (0.293 µM and 0.259 µM) with a sensitivity of 184 nA µM-1 cm-2 and 208 nA µM-1 cm-2 (S/N=3) for HQ and CC, respectively. In addition, the CuS-CNF/GCE shows a selective identification of HQ and CC over potential interfering metal ions (Zn2+, Na+, K+, NO3-, SO42-, Cl-) and organic compounds (ascorbic acid, glucose), and a satisfactory recovery is also obtained in the spiked water samples. These results suggest that the CuS-CNF/GCE can be used as an efficient electrochemical sensor for the simultaneous determination of co-existing environmental pollutants such as HQ and CC in water environments with high selectivity and acceptable reproducibility.

An excited-state Wolff rearrangement reaction of 5-diazo Meldrum's acid: an ab initio on-the-fly nonadiabatic dynamics simulation.

A global switching on-the-fly trajectory surface hopping dynamics simulation at the 3SA-CASSCF(12,11)/6-31G* quantum level has been employed to probe the photo-induced Wolff rearrangement (WR) reaction of 5-diazo Meldrum's acid (DMA) within three low-lying electronic excited states. The present simulation predicted that the branching ratios for relaxing back to the ground state, isomerizing to diazirine, and reaction to ketene I via carbene I are 69% ± 0.1, 3% ± 0.4, and 28% ± 0.1, which are in excellent agreement with those obtained by the femtosecond spectroscopy experiment, 67%, 3% and 30%, respectively. In particular, the present simulation revealed that the major WR reaction to ketene I pathway is stepwise via the excited-state to carbene I (17.8% ± 0.2) and via the ground-state to carbene I (8.7% ± 0.2), and the minor pathway is concerted synchronous (1.5% ± 0.6). The photo-induced WR reaction of DMA has been quantitatively interpreted in terms of the distribution of extended seam surfaces as a function of CN dissociation bonds for two important conical intersections within three low-lying electronic excited states. Ultrafast dynamic time constants have been estimated to be about 500 fs ± 120 fs and 180 fs ± 80 fs for the stepwise and the concerted WR reaction to ketene I which are also in good agreement with those determined by the experiment. Therefore, the photo-induced excited-state WR reaction mechanism has been quantitatively revealed by the present real-time dynamics simulation.

Ultrafast intersystem crossing for nitrophenols: ab initio nonadiabatic molecular dynamics simulation.

Ultrafast intersystem crossing mechanisms for two p- and m-nitrophenol groups (PNP and MNP) have been investigated using ab initio nonadiabatic molecular dynamics simulations at the 6SA-CASSCF level of theory. Trajectory surface hopping simulation has been performed within an intersystem crossing network constructed from two low-lying singlets (S0 and S1) and two low-lying triplets (T1 and T2). It is found that the dominant relaxation S1 → T2 pathway accounts for 65.4% (85.0%) of the quantum yield with a time constant of 13.4 fs (22 fs) and the S1 → T2 → S0 pathway accounts for 33.1% (13.5%) with a time constant of 275 fs (375 fs) for PNP (MNP). In comparison with the previously studied excited-state proton transfer process for ONP, the dominant relaxation S1 → T2 → T1 pathway accounts for 49.3% with a time constant of 40 fs and the S1 → T2 → T1 → S0 pathway accounts for 47.5% with a time constant of 300 fs. The relaxation mechanisms and electronic structures of the intersystem crossings are in close relation with the relative motion between the torsion motions of the nitro-group and the hydroxyl group. The present simulation provides new physical insight for understanding ultrafast photochemical intersystem crossing dynamics.

Probing the π → π* photoisomerization mechanism of trans-azobenzene by multi-state ab initio on-the-fly trajectory dynamics simulations.

Global nonadiabatic switching on-the-fly trajectory surface hopping simulations at the 5SA-CASSCF(6,6)/6-31G quantum level have been employed to probe the photoisomerization mechanism of trans-azobenzene upon ππ* excitation within four coupled singlet low-lying electronic states (S0, S1, S2, and S3). We have performed 586 sampling trajectories (331 starting from S2 and 255 from S3), and we found about half of the sampling trajectories staying on S1 or S2 states as resonances and the other half of them ending on the ground S0 state as active trajectories. The present simulation has demonstrated that there are six distinct photoisomerization pathways which can be summarized as three categories; one is the newly opened inversion-inversion nonreactive isomerization pathway accounting for 40% (34%) of active trajectories at a time constant of 80 fs (320 fs), the other is the inversion-torsion reactive and nonreactive isomerization pathways accounting for 40% (20%) of active trajectories at a time constant of 880 fs (1700 fs), and the third is the torsion-torsion reactive and nonreactive isomerization pathways accounting for 20% (46%) of active trajectories at a time constant of 780 fs (1000 fs) upon S2 (S3) ππ* excitation. The simulated total reactive quantum yield for trans-azobenzene photoisomerization upon S2 (S3) ππ* excitation is about 0.11 (0.13) which is in good agreement with recent experimental results of 0.09-0.20. Furthermore, the newly opened inversion-inversion nonreactive isomerization pathway from the present simulation agrees well with cascade experimental measurements of the Sn → S1 → S0 relaxation mechanism in both branching ratio and time constant.

Study on the mechanism of platinum(ii)-catalyzed asymmetric ring-opening addition of oxabicyclic alkenes with arylboronic acids.

The mechanism of an asymmetric ring-opening (ARO) addition of oxabicyclic alkenes catalyzed by a platinum(ii) catalyst was investigated by M06-2X/6-311G(d,p) using density functional theory (DFT). All the structures were optimized in the solvent model density (SMD) solvation model (solvation = the mixture of H2O/CH2Cl2 1 : 10, v/v) for consistence with experimental conditions. The overall mechanism is considered as a four-step reaction including transmetalation, carboplatinum, ß-oxygen elimination, and hydrolysis. The transmetalation and carboplatinum steps are multi-step processes, and both the regioselectivity and the enantioselectivity lie in the carboplatinum process. Based on the natural population analysis (NPA) and the orbital composition analysis of oxabicyclic alkenes, the preferable coordination site with a platinum(ii) center is considered as the bridging oxygen atom by exo-coordination because of the less steric hindrance and the stronger electronic effect. This coordination is thought of as origin of the regioselectivity and the enantioselectivity, which is different from that proposed previously. The Gibbs free energy profiles show that the rate-determining step involves the migration of an aryl group from the platinum(ii) center to one of the closer enantiotopic carbon atoms in an alkene of the oxabicyclic alkenes. The theoretically predicted enantiomeric excess (ee) value of 82% for this reaction is very close to the experimental ee value of 80%. It was found that the hydrogen bonds between the oxabicyclic alkenes and water molecules promotes the platinum(ii) catalyst leaving the reaction system effortlessly and entering the next catalysis recycle. In the overall catalytic cycle, the highest free energy barrier is 30.1 kcal mol-1 and the process releases an energy of 26.3 kcal mol-1. The results confirm that the Pt(ii)-catalyzed ARO reactions take place at mild experimental conditions, which is consistent with the experiment observations. Thus, this study is important for understanding the catalytic behavior of the transition metal platinum(ii) in an asymmetric ring-opening reaction.