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[Display omitted] Replacing an oxygen atom with one of the boron atoms in a 5-membered B-Heterocyclic carbene and its Si and Ge congeners (BHEs; E = C, Si, Ge) creates Boron-Oxygen-Heterocyclic divalents (BOHEs) which may have potential uses as organometallic ligands. In addition to a survey on their singlet–triplet energy gap (ΔE T-S) for the stability concerns, the nature of the E–M bonds in XBOHE–MCl complexes (M = CuI, AgI, AuI; E = C, Si, Ge; X = F, Cl, Br) is theoretically investigated using the natural bond orbital (NBO), energy decomposition analysis (EDA), and extended transition state natural orbital for chemical valence (ETS-NOCV) analysis. The outcomes show interesting stabilities of singlet/triplet configurations in carbenes, silylenes, and germylenes. Also, the results exhibit that the E–M bonds in the complexes have a higher electrostatic character. [ABSTRACT FROM AUTHOR]

Thermally Activated Delayed Fluorescent (TADF) molecules with Donor (D) -Acceptor (A) –Donor-Acceptor π-Conjugated Macrocycle structures have broad application potential in organic light-emitting diodes. In this paper, three D−A line type and one D−A−D−A π‑Conjugated Macrocycle molecules with same donor and acceptor groups are investigated using polarizable continuum model (PCM) combined with density functional theory (DFT) and time-dependent functional theory (TD-DFT) in solvent and film. It is found that the macrocyclic structure has a smaller energy gap (ΔEST) between the first singlet excited state (S1) and the first triplet excited state (T1) than the linear structure. The TADF property is also analyzed based on the calculation of spin–orbit coupling (SOC) and the (reverse) intersystem crossing (RISC) rates between S1 and T1. The macrocyclic molecules have larger SOC and faster RISC rates, which also well explains the experimental predictions and results. [Display omitted] • The macrocyclic structure has smaller △ES1-T1 as compared to the linear structure. • The macrocyclic molecules have larger SOC and faster RISC rates, which also well explains the experimental predictions and results. • Compared to the linear structure, the macrocyclic structure has a smaller reorganization energy and H-R factor. Thermally Activated Delayed Fluorescent (TADF) molecules with Donor (D) -Acceptor (A) –Donor-Acceptor π-Conjugated Macrocycle structures have broad application potential in organic light-emitting diodes. In this paper, three D − A line type and one D − A − D − A π‑Conjugated Macrocycle molecules with same donor and acceptor groups are investigated using polarizable continuum model (PCM) combined with density functional theory (DFT) and time-dependent functional theory (TD-DFT) in solvent and film. It is found that the macrocyclic structure has a smaller energy gap (ΔE ST) between the first singlet excited state (S 1) and the first triplet excited state (T 1) than the linear structure. The TADF efficiency is also analyzed based on the calculation of spin–orbit coupling (SOC) and the (reverse) intersystem crossing (RISC) rates between S 1 and T 1. The macrocyclic molecules have larger SOC and faster RISC rates, which also well explains the experimental predictions and results. [ABSTRACT FROM AUTHOR]

[Display omitted] • Forty kinds of keto-RDX based derivatives containing different substituents were designed and have been optimized at the B3LYP-D3/6-311G** level. • Horizontal comparison of A and B series derivatives showed that the number of substituents affected the thermal stability of the material. • All the compounds have very high detonation performance, which is better than HMX and RDX. Forty kinds of keto-RDX based derivatives containing different substituents (for instance –NHNH 2 , -C(NO 2) 3 , –NHNO 2 , –NO 2 and –ONO 2) were designed and have been optimized at the B3LYP-D3/6-311G** level. The effects of single and multiple substituents on the properties of these energetic materials were analyzed. The electronic structure, energy gap, heat of formation, detonation performance, thermal stability, thermodynamic parameters and surface electrostatic potential of the compounds were systematically studied. Compared with the traditional energetic compounds HMX (D = 9.10 km s−1, P = 39.0 GPa) and RDX (D = 8.75 km s−1, P = 34.0 GPa), most of the derivatives designed in this paper have higher detonation velocity and detonation pressure. Among them, the largest density, detonation velocity, and detonation pressure are 2.14 g cm−3 (B6), 10.95 km s−1 (D2), and 57.81 GPa (E7), respectively. Combined with surface electrostatic potential analysis, seven keto-RDX based derivatives of C1 , C4 , C5 , E3 , E4 , E5 , and E7 that can be selected as promising high energy density materials were finally picked out. [ABSTRACT FROM AUTHOR]

In this work, we systematically study the photo physical properties for NIR-AIE-TADF molecules in toluene solvent, film and crystal by PCM and QM/MM method, respectively. First, the molecular luminescence was red-shifted by about 100 nm, when –CH3 in the molecule is replaced by –OCH3, which may be due to the increased vibrational intensity of the molecule, resulting in energy dissipation. Second, the vibrations were effectively suppressed in the solid state for both TBSMCN and O-TBSMCN molecules, which is the reason for the AIE of the molecules. Third, the molecules have a small △ES1-T1 in the solvent with TADF properties, and their △ES1-T1 is reduced and SOC is increased in the solid state, which is more favorable for the RISC. Fourth, by analyzing the nature of the transitions in the dimers in the film structure we find that O-TBSMCN molecule undergoes intermolecular charge transfer, which may be one of the reasons for its reduced film efficiency. [Display omitted] • The inhibition of vibration in the aggregated state is the main reason for AIE. • A smaller △E S1-T1 and a larger SOC in aggregate state, it is favorable for RISC. • The O-TBSMCN molecule undergoes intermolecular CT, which lower its film efficiency. TADF emitters with both high exciton utilization and luminescence efficiency show promising applications in OLEDs, especially it with AIE characteristics. However, theoretical studies on emitters with amorphous structure with the consideration of the solid-state effect are limited. In this work, a multi-scale simulation is performed to study the reported compounds TBSMCN and O-TBSMCN, which both possess distinct features of NIR-AIE-TADF. The packing modes of the molecules in film and crystal are obtained by molecular dynamics simulations (MD) and experiments, and then the photo physical properties are studied by using the QM/MM method. The results show that geometrical changes between the ground state (S 0) and the first singlet excited state (S 1) are restricted in aggregate state. Thus, the non-radiative energy consumption process is hindered, this indicates the AIE mechanisms. Second, the molecules exhibit a smaller △E S1-T1 and a more significant SOC in aggregate state, which is more favorable for the RISC. Finally, by analyzing the NTO of the dimers in the film, the O-TBSMCN molecule undergoes intermolecular charge transfer, which may be one of the reasons for the significant reduction in its film efficiency. Our calculations could help one to better understand the NIR-AIE-TADF mechanism from a theoretical perspective. [ABSTRACT FROM AUTHOR]

The mechanism of the reaction of CH 3 COCl with HNO has never been investigated by theoretical and experimental methods before, which is explored in this contribution. The geometries are optimized at the BMK/6-311+G(d,p) level. On the basis of the optimized geometries, the energy is further refined at the BMC-CCSD level. Finally, twenty-five pathways and corresponding possible products are located including the cleavage of N H, C C, C H, and C Cl bonds and formation of O H, O Cl, O N, O C, N Cl, N H, N C, H H, and H Cl bonds. However, most of reaction pathways are impossible because of the higher barrier heights and positive reaction energy. The most favorable pathway is the N H1 and C Cl bonds rupture and H1 Cl bond formation leading to products CH 3 CONO and HCl. [ABSTRACT FROM AUTHOR]

The mechanism of chloroacetyl chloride (CH 2 ClCOCl) decomposition has never been investigated by theoretical and experimental methods before, which is explored at the BMC-CCSD//BMK/6-311+G(d, p) level in this work. Eight pathways and ten transition states are located to search for more favorable pathways. Some dissociated pathways start from the trans-CH 2 ClCOCl directly. Alternatively, the trans-CH 2 ClCOCl would transform to the cis-CH 2 ClCOCl. Then, the cis-CH 2 ClCOCl would dissociate into the product with single or multi steps. Starting from the trans-CH 2 ClCOCl, P1 (CHClCO + HCl) is the most favorable product by the rupture of C1 H1 bond and C2 Cl2 bond and the formation of H1 Cl2 bond (Pathway 1), due to the least step and the lowest barrier height. P2 (CH 2 Cl 2 + CO) is the common product of both Pathway 2 and Pathway 4 those start from the trans- and cis-CH 2 ClCOCl, respectively. Owing to the second lowest rate-determining barrier height, P2 is the second feasible product. P3 (CH 2 Cl(O)CCl) formed by the migration of O atom from C2 atom to Cl1 atom is the most minor product because of the highest barrier height. Other products P4 (CH 2 Cl + CO + Cl), P5 (CH 2 CO + Cl 2 ), and P6 (CH 2 ClCO(Cl)) formed by the attack of Cl2 atom to C1 atom, Cl1 atom, and O atom, respectively, are not energetically accessible because of higher barrier-consumed and/or complicated process. [ABSTRACT FROM AUTHOR]

The hydrated complexes of cyclo(L-pro) 4 -M + (M + = Li + , Na + , K + , Rb + and Cs + ) have been studied in the gas phase at B3LYP/6-31+G(d) with n = 4–6 water molecules. The effect of microsolvation on the stability of these complexes has been studied, too. The stability of these complexes increases in the order Li + > Na + > K + > Rb + > Cs + . The hydrated complexes are more stable than the unhydrated complexes in the gas phase. The optimized structures have been used to perform natural bond orbital (NBO) analysis. The highest interaction energies are seen in the Li + complexes. The topological properties of the microhydrated complexes at bond critical points (BCP) are also considered by AIM analysis. [ABSTRACT FROM AUTHOR]

Several octahedral iron complexes that contain two lateral diamondoid (formerly called nanodiamond) units (joined by terminal COO 1− groups) have been proposed. All newly proposed coordination species reach a stable configuration. The nature of the apical substituents (H 2 O, NH 3 , CO, CN 1− , NO) accounts for the change in properties of the resultant compounds, therefore those compounds containing H 2 O or NH 3 ligands manifest a scheme of chemical properties similar to their analogues as coordination compounds. Furthermore the complexes containing CO or CN 1− ligands fulfill the typical description of organometallic species, whereas the complexes with the NO ligand, in their three manifestations, range between both behaviors and are studied as a special case. However, in all cases, the diamondoid ligands work as insulator walls restricting electronic movements to the regions which accommodate the metallic center, the apical ligands and the terminal COO 1− groups. The nature of the molecular orbitals scheme shows wide variation that ranges between insulator and conductor behavior. [ABSTRACT FROM AUTHOR]

The detailed potential energy surface for the reactions of Criegee intermediate (CI, CH 2 OO) with acetaldehyde (CH 3 CHO) has been investigated at CCSD(T)/AUG-cc-pVTZ//B3LYP/6-311++G(2d,2p) level of theory. The results show that the feasible products are HCHO + CH 3 COOH, HCOOH + CH 3 CHO or HCHO + CH 3 CHOO obtained by different channels. These studies can explain the mechanism of the formation of the products obtained by the experiment. [ABSTRACT FROM AUTHOR]

Computational investigations on the gas phase S N 2 reactions of X ions ( X - = OH - , F - , Cl - , Br - , and I - ) with fluoroethane and 2-fluoroethanol (β-hydroxyl ethyl fluoride) were performed by using MPW1K, M06 and CCSD(T) methods with a range of basis sets including 66-311++G ∗∗ , TZVP, aug-cc-pVDZ and SDD. To better understand the nature of the corresponding intermolecular interactions, we performed natural bond orbital (NBO) analysis and Bader’s quantum theory of atoms in molecules (QTAIM). In our calculations, we took into account two possible pathways for these reactions, i.e. S N 2 reactions of 2-fluoroethanol. In path( i ), β-hydroxyl group participates in hydrogen bonding (H-bonding) with fluoride ion as leaving group in transition state. However, in path( ii ), transition state includes H-bonding between hydroxyl group and nucleophile X − . Results indicate that in comparison with the absence of β-OH substituent i.e. reactions of fluoroethane, the activation barrier decreases in path( i ), but increases in path( ii ). The progress of each pathway depends on H-bonding character of nucleophile and leaving group. In addition, for X - = Cl - we compared β-OH group effect in the gas phase with its effect in dimethyl sulfoxide (DMSO). [ABSTRACT FROM AUTHOR]

A theoretical study on the E and Z isomers of R CH N R′ compounds (R = R′, R ≠ R′; R or R′ = CH 3 , CF 3 , ph or t-Bu) as well as E isomer of R CH N CH 3 and CH 3 CH N R (R = C 60 H or C 60 CH) molecules is reported. NBO analysis and DFT calculations were used to investigate the effect of R and R′ groups on the strength and the nature of C N bond in above imines. The relative stabilities of R CH N R′ and R′ CH N R isomers is also compared. Furthermore, in all compounds the type of π and π * and also HOMO and LUMO molecular orbitals and the energy gap between them is studied. Also three types of anomeric effect in imine compounds having CH 3 , CF 3 , ph or t-Bu substituted groups have been assigned. [ABSTRACT FROM AUTHOR]

Highlights: [•] The suggested compounds are novel and their study can help to develop interesting conductor species. [•] The nanodiamond ligands are insulators but the coordination iron compounds are conductors. [•] The theoretical calculations suggest a stable triplet state. [ABSTRACT FROM AUTHOR]

Highlights: [•] Interaction of some endofullerenes with the hydrated metal cations is reported. [•] The proton transfer occurs from [Al(H2O)6]3+ cation to all studied endofullerenes. [•] The encaged halide anion significantly increases the interaction of C60 with the cations. [•] The [F@C60]− has largest interaction with [Mg(H2O)6]2+ cation. [Copyright &y& Elsevier]

Highlights: [•] Examined thermodynamic properties of ozonation reactions in presence of bromide. [•] High level G4MP2 and G4 theoretical methods employed. [•] Aqueous phase behavior modeled with SMD, PCM, and CPCM solvation models. [•] Results will help improve mechanistic understandings of water treatment. [ABSTRACT FROM AUTHOR]

Abstract: Using density functional theory, the adsorption of NO2 molecule on an AlN nanocone is investigated in terms of energetic, structural, electronic and field emission properties. The NO2 is preferentially chemisorbed on the pentagon of the cone apex, releasing energy of 65.43kcal/mol. The AlNC is transformed from an intrinsic semiconductor with Eg of 2.86eV to extrinsic p-type one with smaller Eg of 1.62–2.34eV upon adsorption processes. The largest reduction of Eg is predicted when the NO2 molecule is adsorbed on a hexagonal ring of the AlNC containing homonuclear N–N bonds. We conclude that the AlNC may transform the presence of the NO2 molecule into an electrical signal. The emitted electron current density from the AlNC surface may be also decreased in the presence of NO2 molecules. We also found that the electronic sensitivity of AlNC to NO2 molecule may be tuneable in the presence of an external electric field. [Copyright &y& Elsevier]

Abstract: The mechanism and kinetic properties of OH-initiated gas-phase reaction of 2;4-dibrominated diphenyl ether (BDE-7) were studied at the MPWB1K/6-311+G(3df;2p)//MPWB1K/6-31+G(d;p) level of theory. Two types of reactions;hydroxyl addition and hydrogen abstraction;were investigated. The calculation results indicate that addition reactions;except for the bromo-substituted one;have lower barriers than hydrogen abstraction reactions. Moreover;hydroxyl radicals are likely to react with phenyl ring without bromine atoms. Rate constants were deduced over 200–1000K using canonical variational transition state theory with small curvature tunneling contribution. At 298K the calculated rate constant for the title reaction is 3.76×10−12 cm−3 molecule−1 s−1. [Copyright &y& Elsevier]

Abstract: The reaction pathways of selenium vapor (Se) with hydrogen selenide (H2Se) have been investigated theoretically on the triplet and singlet potential energy surfaces. All species for title reaction have been optimized at the UMP2(FC)/6-311++G(d, p) computational level. The energetic data have been obtained at the UCCSD(T)//UMP2 level employing the cc-pV5Z basis set. Three initial collision complexes, 3IN1 (Se–SeH2), 3IN2 (Se–HSeH) and 1IN1 (Se–SeH2) have been considered for the Se-atom with H2Se reaction on the triplet and singlet potential energy surfaces. Four kinds products HSeSeH, HSe+HSe, H+HSe2 and Se2 +H2 are obtained through variety of transformations of initial reactants and complexes. Calculations reveal that there exist two intersystem crossings between the triplet and singlet potential energy surfaces. Also, the investigation of Se+H2Se reaction paths shows that reaction initiates on the triplet potential energy surface and continues on both triplet and singlet (through intersystem crossing) potential energy surfaces to form the main product of HSeSeH. [Copyright &y& Elsevier]

Abstract: The influence of the structure of diphosphine ligands on copper fluoride and copper (I) hydride complexes has been investigated by a theoretical DFT study. For both complexes, two stable structures appear. A near “symmetric” one, with both phosphorus lone pairs coordinated to the copper atom, and an “asymmetric” with a single phosphorus atom linked to the copper atom. Three interactions influence the stability of one situation over the other. Although the higher ligand deformation energy observed for the near symmetric complexes is compensated by the increased stability due to the second metal-phosphorus bond, a supplementary hydrogen bond interaction observed for the copper fluoride complexes, leads to a more important stabilization of the asymmetric complexes. The presence of multiple stable catalytic structures is most likely of importance for the reactivity of the catalytic reactions involving copper hydride or copper fluoride catalysts. [ABSTRACT FROM AUTHOR]

Abstract: The insertion reactions of the silylenoid H2SiLiF into Si–X bonds (X=F, Cl, Br) have been studied by ab initio and DFT calculations. The results indicate that the insertions proceed in a concerted manner, forming H2SiXCH3 and LiF. The essence of these reactions are the donations of the electrons of X into the p orbital on the Si atom in H2SiLiF and the σ electrons on the Si atom in H2SiLiF to the positive SiH3 group. The order of reactivity by H2SiLiF insertion indicates the reaction barriers increase for the same-family element X from top down in the periodic table. All the insertions are exothermic reactions. [ABSTRACT FROM AUTHOR]

Abstract: Density functional theory calculations reveal that iron(IV)-oxo porphyrin cation radical (Cpd I) models are indeed much more reactive than iron(IV)-oxo porphyrin (Cpd II) models in the case of 1,3-cyclohexdiene oxidation. The geometrical parameters and electronic configuration are quite different for Cpd I and Cpd II. This is the origin of the reactivity difference. The axial ligand indeed affects the geometries of Cpd I and Cpd II and the oxidation process, even though it cannot switch the reactivity of Cpd I and Cpd II. Interestingly, the axial ligand can switch the oxidation process from dehydrogenation to epoxidation by Cpd I, however, for Cpd II, it cannot switch the reaction process, but lessen the barrier difference of dehydrogenation and epoxidation, even though the decrease of barrier is not significant. The axial ligand effect is somewhat in relation to the Hammett substituent parameter (σ P) of the substituent group in the axial ligand. The more negative the σ P is, the longer the Fe Cpd I is, and the higher the reaction barrier is. [ABSTRACT FROM AUTHOR]

Abstract: The structures, energetics, spectroscopies, and isomerization of the doublet Si2PO radical are explored at various levels. At the UB3LYP/6-311+G(2df) level, a total of 12 minimum isomers and 15 interconversion transition states are located. Four cyclic isomers are found to be thermodynamically and kinetically stable at the higher UCCSD(T)/6-311++G(2df)//UM062x/6-311+G(2df)+ZPVE and may be experimentally or astrophysically observable. The lowest-lying isomer 1 c-SiOSiP (2B2) (0.0kcal/mol) corresponds to a rhomboidal-type structure similar to the global state of Si2NO, followed by another three-membered ring isomer 3 O-cSiSiP (2A′) (23.1kcal/mol) which is similar to the global state of [Si, C, P, O]. Another two stable isomers are the three-membered ring isomers 11 P-cSiSiO (35.0kcal/mol) and 6 O-cPSiSi (47.5kcal/mol), respectively. The bonding nature of the four isomers is analyzed. Meanwhile, the calculated results are compared with its analogs SiCPO, Si2NO, and Si2PS. Implications in the laboratory and interstellar space are also discussed. The predicted structures and spectroscopic properties are expected to be informative for the identification of Si2PO in the laboratory and space. [ABSTRACT FROM AUTHOR]

Abstract: The complete catalytic cycle of the reaction of glucose conversion to 5-hydroxymethylfurfural (HMF) by metal chlorides (MCl3) in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid has been studied using density functional theory (DFT) calculations. Insights into the most preferred mechanistic pathways were gained for both isomerization of glucopyranose to fructofuranose as well as subsequent dehydrations of fructofuranose to the final product HMF, which were considered as two main reactions in the whole process. The first part of the mechanism was predicted to proceed slowly and thermodynamically less favored. A five-membered-ring chelate complex of the metal atom with glucopyranose was assumed as a key intermediate. The second part consists of sequential releases of three water molecules from fructofuranose. The removal of the first water appears to be rate controlling, whereas further loss of the second and third water were highly exothermic. A variety of transition metal cations in the same oxidation states (WCl3, MoCl3, and FeCl3) were screened and parallel DFT studies were carried out to determine their reactivities in the catalytic reaction. It turns out that the metal centers exerted significant influences on the stabilities of the intermediates as well as the energy barriers associated with each elementary reaction step. The overall free energy barriers at 353K indicated that the reaction activities of the entire processes over different MCl3 active sites decrease in the order of WCl3 >MoCl3 >CrCl3 >FeCl3, in which WCl3 may be the most promising catalyst at low temperatures. [ABSTRACT FROM AUTHOR]

• The electronic properties of MoS 2 sheets upon embedding Ag atoms was investigated by DFT calculations. • The increase of the electronic density between the Ag and S atoms indicate the formation of chemical bonds. • The adsorption of gases on Ag-MoS 2 sheets is more energetically favorable than that on the pristine ones. By using first principles calculations, we studied the electronic, and structural properties of MoS 2 monolayers adsorbed with Ag noble metals. In this regard, we have estimated the adsorption energies to further elaborate the stability of the obtained structures, and the electronic properties such as charge density differences and density of states. The results suggest that the adsorption of Ag atoms on MoS 2 monolayers gives rise to the stable configurations with relaxed structure. We have evaluated the interaction of diverse gas molecules with intrinsic and Ag-adsorbed MoS 2 systems. Our calculated results suggested that the interaction of gas molecules with Ag-adsorbed MoS 2 nanosheets is more favorable than that with non-adsorbed nanosheets. Thus, the Ag-adsorbed MoS 2 nanosheets showed great capability as chemical sensors. By analyzing the projected density of states of the Ag-MoS 2 system and gas molecules, we found that a chemisorption phenomenon occurs at the interface area. [ABSTRACT FROM AUTHOR]

Abstract: Gas phase geometries and strain energies (E S ) at 298.15K and 1atm were calculated using the G4MP2 composite method and various density functional model chemistries for tetracyclo[3.3.3.13,10 .17,10]tridecane (bowlane) and its methylene spacer edge and lip expanded (−CH2−) n (n =1–4) homologs. Enthalpies of formation were also estimated using the atomization method for bowlane and its single methylene edge spacer homolog. Calculated E S are strongly dependent on the choice of functional, varying up to 62kJ/mol for a particular compound with different theoretical methods. Lip spacers have a significantly lower absolute effect on E S than edge spacers. Sequential additions of methylene lip spacers progressively decreases the strain energy of bowlane derivatives, whereas edge spacing results in a more complex E S relationship that depends on the number and geometrical arrangement of the spacers. [ABSTRACT FROM AUTHOR]

Relative energies of the stationary points for CH 3 OH+HO 2 reaction at the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ level of theory. • Master equation (ME) was utilized to simulate the collision between CH 3 OH with HO 2 radical at the presence of bath gas. • The reaction mechanism explored through the lowest doublet potential energy surface at CCSD (T)/aug-cc-pVTZ//B3LYP/ aug-cc-pVTZ level of theory. • Lifetime of CH 3 OH.HO 2 intermediate (INT*) is short due to its shallow potential depth. • At high pressure, the INT* is thermalized and equilibrates with the bath gas that equilibrium constant is well-defined. • ME predicts the formation of CH 2 OH + H 2 O 2 and CH 3 O + H 2 O 2 as the major products. Master equation (ME) with Lennard-Jones potential utilized to simulate the collision between CH 3 OH and HO 2 radical in the presence of bath gas. The reaction mechanism explored through the lowest doublet potential energy surface at CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ level of theory that is barrierless and forms shallow energized intermediate at the entrance channel. The investigation of the fractional population showed that lifetime of CH 3 OH.HO 2 intermediate (INT*) is fairly short due to its shallow depth, and at the low temperature, most reaction takes place by re-dissociation back to reactants and also when the pressure is high enough, the INT* is thermalized and comes into equilibrium with the bath gas, so that equilibrium constant is well-defined that is in accordance with Christiansen's results. The rate constant of products agrees with reported experimental values in literature. ME predicts the formation of CH 2 OH + H 2 O 2 and CH 3 O + H 2 O 2 as the major products; these results agree with previous studies. [ABSTRACT FROM AUTHOR]

• The reaction path is theoretically studied. • The reaction mechanism is elucidated. • A new reaction path is proposed. Palladium(II) complexes are important in organometallic chemistry because they are easily stored and handled due to their electrophilicity and solubility in most common organic solvents. Here, we study the potential energy surface of the reaction of Pd(II)-catalyzed nucleophilic addition initiated by aminopalladation using density functional theory calculations and elucidate its mechanism. The results show that the reaction paths suggested in He et al. [32] are unlikely to occur due to the high energy of their reaction barriers. We also propose a new reaction path that can produce the corresponding products. [ABSTRACT FROM AUTHOR]