Lowest singlet and triplet potential energy surfaces of S2N2

Forty four stationary points have been located on the lowest singlet and triplet potential energy surfaces of S(2)N(2). Ten minima and ten saddle points on the lowest singlet surface and eleven minima and thirteen saddle points on the lowest triplet surface were found. All saddle points were connected to minima or lower-order saddle points by following the intrinsic reaction coordinate. Renner-Teller effects in the linear isomers were studied by examining their bending curves. The S(2)N(2) polymerization mechanism was investigated by first locating the transition state corresponding to ring opening and then considering all species connected to it that are close in energy. The commonly accepted mechanism is problematic due to the number of species that would lead to dissociation to SN + SN. Other possible isomers that are consistent with the experimental evidence but do not connect to SN radicals in the dissociation limit were examined. A mechanism of polymerization to (SN)(x)() is proposed that involves excitation of the square planar singlet molecule to the triplet surface. The triplet species then undergoes a puckering, and polymerization occurs in a direction approximately perpendicular to the S(2)N(2) plane. Consideration of the predicted vibrational frequencies suggests the structure of the second isomer of S(2)N(2). This isomer has a trans-NSSN structure with a long SS bond. The energetics of trans-NSSN are consistent with the observed temperature effects in the dimerization of SN. Analysis of the bending curves of linear NSSN and NSNS indicates that trans-NSSN is the only isomer which has a small yet significant barrier to that dimerization.     

Ab initio potential energy surfaces and nonadiabatic interactions in the H+ +NO collision system

Ab initio calculations on the H(+)+NO system have been carried out in Jacobi coordinates at the multireference configuration interaction level employing Dunning's correlation-consistent polarized valence triple zeta basis set to analyze the role of low-lying electronic excited states in influencing the collision dynamics relevant to the experimental collision energy range of 9.5-30 eV. The lowest two adiabatic potential energy surfaces, asymptotically correlating to H(+)+NO(X (2)Pi) and H((2)S)+NO(+)(X (1)Sigma(+)), have been obtained. Using ab initio procedures, the (radial) nonadiabatic couplings and the mixing angle between the lowest two electronic states (1 (2)A' and 2 (2)A') have been obtained to yield the corresponding quasidiabatic potential energy matrix. The strengths of the computed vibrational coupling matrix elements reflect a similar trend, as has been observed experimentally in the magnitudes of the state-to-state transition probability for the inelastic vibrational excitations [J. Krutein and F. Linder, J. Chem. Phys. 71, 559 (1979); F. A. Gianturco et al., J. Phys. B 14, 667 (1981)].     

Mechanism and rate constants for ammonia photochemical oxidation with O2 on the singlet and triplet potential energy surfaces

The mechanism and thermodynamic of NH₃ + O₂ reaction on the singlet and triplet potential energy surfaces (PES), were carried out using the RMP2 and CCSD (T)//RMP2 theoretical approaches in connection with the 6-311++G(d, p) basis set. Three pre-reactive complexes, ¹C1, ¹C2, and ³C1 on the singlet and triplet PES were formed between ammonia and molecular oxygen. With variety of pre-reactive complexes, six types of products are obtained, of which two types are found to be thermodynamically stable. The mechanistic properties of all products channels are discussed. Results show that production of HONO + H₂ and HN(OH)₂ are the main reaction channels in thermodynamic viewpoint with the Gibbs free energy of ?G° = ?34.681 and ?27.153 kcal/mol, respectively. Rate constants of the title reaction over the temperature range of (200–1000 K) show kinetic products are different from thermodynamic products.     

Theoretical characterization of photoisomerization channels of dimethylpyridines on the singlet and triplet potential energy surfaces

Photoexcitations and photoisomerizations due to low-lying n pi* and pi pi* excited states of dimethylpyridines are investigated by density functional theory, CASSCF, CASPT2 and MRCI methodologies. Mechanistic details for the formation of Dewar dimethylpyridines and the interconversions of dimethylpyridines are rationalized through the characterization of minima and transition states on the singlet and triplet potential energy surfaces of relevant intermediates. Our present theoretical schemes suggest that Mobius dimethylpyridine intermediate 14 and azabenzvalene intermediate 10 can serve as possible precursors to Dewar dimethylpyridines and singlet phototransposition products, respectively. The calculations suggest that an S1(pi pi*)/S0 conical intersection in dimethylpyridines 2 is involved in the formation of 14. An azabenzvalene 10 might be formed through S2(pi pi*)/S1(n pi*) interaction followed by an S1/S0 decay in dimethylpyridine 6. Calculated barriers of isomerizations from 14 to Dewar dimethylpyridine 7 and from 10 to 4 are 8.4 and 28.5 kcal mol(-1) at the B3LYP/6-311 G** level, respectively. In the suggested triplet multistage transposition mechanism, an out-of-plane distorted geometry 19 due to vibrational relaxation of the T1(3B1) excited state of 3,5-dimethylpyridine 6 is a precursor of the interconversion of 6 to 2.4-dimethylpyridine 4. The formation of a triplet azaprefulvene 21 with a barrier of 20.7 kcal mol(-1) is a key step during the triplet migration process leading to another out-of-plane distorted structure 27. Subsequent rearomatization of 27 completes the interconversion of 6 with 4. Present calculations provide some insight into the photochemistry of dimethylpyridines at 254 nm.     

Ab initio potential energy surface of the lowest triplet BH+2 collision complex

Important parts of the lowest triplet potential energy surface of the BH⁺₂ molecular system are studied at the ab initio level. Obtained topological parameters of this surface and regions of its crossing with excited surfaces are compared with results of the DIM method and with previous ab initio studies.     

Theoretical studies of the reaction channels on the SO2/OH/NO singlet potential energy surface

Ab initio MP2/6-311++G(2d,2p) investigation of the SO2/OH/NO singlet potential energy surface (PES) has been performed with the aim to localize and describe the existing minima and transition states linking them. The systematic studies have revealed seven minima, with the trans-HONO-SO2 complex (1t) being the global minimum. Eight transition states between minima or between minima and the relevant reactant species have been described. Several available izomerization and dissociation routes have been identified and discussed. The most favorable association of HOSO2 and NO was found to be a barrierless process forming nitrososulfonic acids. Isomerizations between trans-, cis-, and gauche- nitrososulfonic acids (2t, 2c, and 2g) are possible with low-energy barriers. The HOSO2 and NO species can also react via another channels involving high-energy transition states to produce the HOSO-NO2 (3) and HNO-SO3 (4) complexes.     

Computational mechanistic study of methanol and molecular oxygen reaction on the triplet and singlet potential energy surfaces

The reaction of CH₃OH with the O₂ on the triplet and singlet potential energy surfaces (PES) was carried out using the B3LYP, MP2, and CCSD(T)//B3LYP theoretical approaches in connection with the 6-311++G(3df–3pd) basis set. Three pre-reactive complexes, ¹C1, ¹C2, and ³C1, on the singlet and triplet PES were formed between methanol and molecular oxygen. From a variety of the complexes, seven types of products are obtained, of which four types are found to be thermodynamically stable. Results reveal that there exists one intersystem crossing between triplet and singlet PES. For P4 adduct that is the main and kinetically the most favorable product, the rate constants are calculated in the temperature range of 200–1,000 K in the reliable pathway.     

The lowest-lying electronic singlet and triplet potential energy surfaces for the HNO-NOH system: energetics, unimolecular rate constants, tunneling and kinetic isotope effects for the isomerization and dissociation reactions

The lowest-lying electronic singlet and triplet potential energy surfaces (PES) for the HNO-NOH system have been investigated employing high level ab initio quantum chemical methods. The reaction energies and barriers have been predicted for two isomerization and four dissociation reactions. Total energies are extrapolated to the complete basis set limit applying focal point analyses. Anharmonic zero-point vibrational energies, diagonal Born-Oppenheimer corrections, relativistic effects, and core correlation corrections are also taken into account. On the singlet PES, the (1)HNO → (1)NOH endothermicity including all corrections is predicted to be 42.23 ± 0.2 kcal mol(-1). For the barrierless decomposition of (1)HNO to H + NO, the dissociation energy is estimated to be 47.48 ± 0.2 kcal mol(-1). For (1)NOH → H + NO, the reaction endothermicity and barrier are 5.25 ± 0.2 and 7.88 ± 0.2 kcal mol(-1). On the triplet PES the reaction energy and barrier including all corrections are predicted to be 7.73 ± 0.2 and 39.31 ± 0.2 kcal mol(-1) for the isomerization reaction (3)HNO → (3)NOH. For the triplet dissociation reaction (to H + NO) the corresponding results are 29.03 ± 0.2 and 32.41 ± 0.2 kcal mol(-1). Analogous results are 21.30 ± 0.2 and 33.67 ± 0.2 kcal mol(-1) for the dissociation reaction of (3)NOH (to H + NO). Unimolecular rate constants for the isomerization and dissociation reactions were obtained utilizing kinetic modeling methods. The tunneling and kinetic isotope effects are also investigated for these reactions. The adiabatic singlet-triplet energy splittings are predicted to be 18.45 ± 0.2 and 16.05 ± 0.2 kcal mol(-1) for HNO and NOH, respectively. Kinetic analyses based on solution of simultaneous first-order ordinary-differential rate equations demonstrate that the singlet NOH molecule will be difficult to prepare at room temperature, while the triplet NOH molecule is viable with respect to isomerization and dissociation reactions up to 400 K. Hence, our theoretical findings clearly explain why (1)NOH has not yet been observed experimentally.     

Ab initio calculations on the singlet and triplet energy surfaces for CsiH2

Singlet and triplet calculations, including configuration interaction, are reported for H₂CSi, HCSiH and CSiH₂, and for the transition state on both surfaces.     

Quasiclassical trajectory calculations of the reaction C+C2H2-->l-C3H, c-C3H+H, C3+H2 using full-dimensional triplet and singlet potential energy surfaces

Full-dimensional, density functional theory (B3LYP/6-311g(d,p))-based potential energy surfaces (PESs) are reported and used in quasi-classical calculations of the reaction of C with C(2)H(2). For the triplet case, the PES spans the region of the reactants, the complex region (with numerous minima and saddle points) and the products, linear(l)-C(3)H+H, cyclic(c)-C(3)H+H and c-(3)C(3)+H(2). For the singlet case, the PES describes the complex region and products l-C(3)H+H, c-C(3)H+H and l-(1)C(3)+H(2). The PESs are invariant under permutation of like nuclei and are fit to tens of thousands of electronic energies. Energies and harmonic frequencies of the PESs agree well the DFT ones for all stationary points and for the reactant and the products. Dynamics calculations on the triplet PES find both l-C(3)H and c-C(3)H products, with l-C(3)H being dominant at the energies considered. Limited unimolecular reaction dynamics on the singlet PES find both products in comparable amounts as well as the C(3)+H(2) product.     

Kinetic study of the reactions of Br2 with OH and OD

The kinetics of the reactions OH + Br₂ → HOBr + Br (1) and OD + Br₂ → DOBr + Br (3) have been studied in the temperature range 230–360 K and at total pressure of 1 Torr of helium using the discharge‐flow mass spectrometric method. The following Arrhenius expressions were obtained either from the kinetics of product formation (HOBr, DOBr) in excess of Br₂ over OH and OD or from the kinetics of Br₂ consumption in excess of OH and OD: k₁ = (1.8 ± 0.3) × 10⁻¹¹ exp [(235 ± 50)/T] and k₃ = (1.9 ± 0.2) × 10⁻¹¹ exp [(220 ± 25)/T] cm³ molecule⁻¹ s⁻¹. For the reaction channels of the title reactions: OH + Br₂ → BrO + HBr and OD + Br₂ → BrO + DBr, the upper limits of the branching ratios were found to be 0.03 and 0.02 at T = 320 K, respectively. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 698–704, 1999     

Reaction of formaldehyde cation with molecular hydrogen: effects of collision energy and H2CO+ vibrations

The effects on the title reaction of collision energy (E(col)) and five H(2)CO(+) vibrational modes have been studied over a center-of-mass E(col) range from 0.1 to 2.3 eV. Electronic structure and Rice-Ramsperger-Kassel-Marcus calculations were used to examine properties of various complexes and transition states that might be important. Only the hydrogen abstraction (HA) product channel is observed, and despite being exoergic, HA has an appearance energy of approximately 0.4 eV, consistent with a transition state found in the electronic structure calculations. A precursor complex-mediated mechanism might possibly be involved at very low E(col), but the dominant mechanism is direct over the entire E(col) range. The magnitude of the HA cross section is strongly, and mode specifically affected by H(2)CO(+) vibrational excitation, however, vibrational energy has no effect on the appearance energy.     

Quasiclassical trajectory calculations of the OH+NO2 association reaction on a global potential energy surface

We report a full-dimensional potential energy surface (PES) for the OH+NO(2) reaction based on fitting more than 55,000 energies obtained with density functional theory-B3LYP6-311G(d,p) calculations. The PES is invariant with respect to permutation of like nuclei and describes all isomers of HOONO, HONO(2), and the fragments OH+NO(2) and HO(2)+NO. Detailed comparison of the structures, energies, and harmonic frequencies of various stationary points on the PES are made with previous and present high-level ab initio calculations. Two hydrogen-bond complexes are found on the PES and confirmed by new ab initio CASPT2 calculations. Quasiclassical trajectory calculations of the cross sections for ground rovibrational OH+NO(2) association reactions to form HOONO and HONO(2) are done using this PES. The cross section to form HOONO is larger than the one to form HONO(2) at low collision energies but the reverse is found at higher energies. The enhancement of the HOONO complex at low collision energies is shown to be due, in large part, to the transient formation of a H-bond complex, which decays preferentially to HOONO. The association cross sections are used to obtain rate constants for formation of HOONO and HONO(2) for the ground rovibrational states in the high-pressure limit.     

Reaction of OH + NO2: high pressure experiments and falloff analysis

High pressure experiments on the OH + NO2 reaction are presented for 3 different temperatures. At 300 K, experiments in He (p = 2-500 bar) as well as in Ar (p = 2-4 bar) were performed. The rate constants obtained in Ar agree well with values which have been reported earlier by our group (Forster, R.; Frost, M.; Fulle, D.; Hamann, H. F.; Hippler, H.; Schlepegrell, A.; Troe, J. J. Chem. Phys. 1995, 103, 2949. Fulle, D.; Hamann, H. F.; Hippler, H.; Troe, J. J. Chem. Phys. 1998, 108, 5391). In contrast, the rate coefficients determined in He were found to be 15-25% lower than the values given in our earlier publications. Additionally, results for He as bath gas at elevated temperatures (T = 400 K, p = 3-150 bar; T = 600 K, p = 3-150 bar) are reported. The results obtained at elevated pressures are found to be in good agreement with existing literature data. The observed falloff behavior is analyzed in terms of the Troe formalism taking into account two reaction channels: one yielding HNO3 and one yielding HOONO. It is found that the extracted parameters are in agreement with rate constants for vibrational relaxation and isotopic scrambling as well as with experimentally determined branching ratios. Based on our analysis we determine falloff parameters to calculate the rate constant for atmospheric conditions.     

Singlet and triplet potential surfaces for the O2+C2H4 reaction

Electronic structure calculations at the CASSCF and UB3LYP levels of theory with the aug-cc-pVDZ basis set were used to characterize structures, vibrational frequencies, and energies for stationary points on the ground state triplet and singlet O(2)+C(2)H(4) potential energy surfaces (PESs). Spin-orbit couplings between the PESs were calculated using state averaged CASSCF wave functions. More accurate energies were obtained for the CASSCF structures with the MRMP2/aug-cc-pVDZ method. An important and necessary aspect of the calculations was the need to use different CASSCF active spaces for the different reaction paths on the investigated PESs. The CASSCF calculations focused on O(2)+C(2)H(4) addition to form the C(2)H(4)O(2) biradical on the triplet and singlet surfaces, and isomerization reaction paths ensuing from this biradical. The triplet and singlet C(2)H(4)O(2) biradicals are very similar in structure, primarily differing in their C-C-O-O dihedral angles. The MRMP2 values for the O(2)+C(2)H(4)→C(2)H(4)O(2) barrier to form the biradical are 33.8 and 6.1 kcal/mol, respectively, for the triplet and singlet surfaces. On the singlet surface, C(2)H(4)O(2) isomerizes to dioxetane and ethane-peroxide with MRMP2 barriers of 7.8 and 21.3 kcal/mol. A more exhaustive search of reaction paths was made for the singlet surface using the UB3LYP/aug-cc-pVDZ theory. The triplet and singlet surfaces cross between the structures for the O(2)+C(2)H(4) addition transition states and the biradical intermediates. Trapping in the triplet biradical intermediate, following (3)O(2)+C(2)H(4) addition, is expected to enhance triplet→singlet intersystem crossing.     

Mechanism and rate constants of the CH2 + CH2CO reactions in triplet and singlet states: A theoretical study

Ab initio and density functional CCSD(T)-F12/cc-pVQZ-f12//B2PLYPD3/6-311G** calculations have been performed to unravel the reaction mechanism of triplet and singlet methylene CH₂ with ketene CH₂CO. The computed potential energy diagrams and molecular properties have been then utilized in Rice–Ramsperger–Kassel–Marcus-Master Equation (RRKM-ME) calculations of the reaction rate constants and product branching ratios combined with the use of nonadiabatic transition state theory for spin-forbidden triplet-singlet isomerization. The results indicate that the most important channels of the reaction of ketene with triplet methylene lead to the formation of the HCCO + CH₃ and C₂H₄ + CO products, where the former channel is preferable at higher temperatures from 1000 K and above. In the C₂H₄ + CO product pair, the ethylene molecule can be formed either adiabatically in the triplet electronic state or via triplet-singlet intersystem crossing in the singlet electronic state occurring in the vicinity of the CH₂COCH₂ intermediate or along the pathway of CO elimination from the initial CH₂CH₂CO complex. The predominant products of the reaction of ketene with singlet methylene have been shown to be C₂H₄ + CO. The formation of these products mostly proceeds via a well-skipping mechanism but at high pressures may to some extent involve collisional stabilization of the CH₃CHCO and cyclic CH₂COCH₂ intermediates followed by their thermal unimolecular decomposition. The calculated rate constants at different pressures from 0.01 to 100 atm have been fitted by the modified Arrhenius expressions in the temperature range of 300–3000 K, which are proposed for kinetic modeling of ketene reactions in combustion. © 2018 Wiley Periodicals, Inc.     

Vertical proton affinities of CH2O and CH2OH+ in their ground singlet,excited triplet and ionized doublet states

Vertical proton affinities were calculated with closed and open shell direct SCF-MO methods for the ground, excited triplet and ionized doublet states of CH₂O and CH₂OH⁺.The computed gas phase basicity of CH₂O follows the order: CH₂O(¹ A ₁) > CH₂O*(³ A ₁ or ³ A ₂) > CH₂O⁺(² B ₂ or ² B ₁).     

The singlet and triplet states of phenyl cation. A hybrid approach for locating minimum energy crossing points between non-interacting potential energy surfaces

The phenyl cation is known to have two low-energy minima, corresponding to ¹ A ₁ and ³ B ₁ states, the first of which is more stable by ca. 25 kcal/mol. The minimum energy crossing point between these two surfaces, located at various levels including a hybrid method first described here, lies just above the minimum of the triplet, 0.12 kcal/mol at the CCSD(T)/cc-pVDZ//B3LYP/SV level, and there is significant spin-orbit coupling between the surfaces at this point. On the basis of these results, the lifetime of the triplet is expected to be very short. Received: 24 October 1997 / Accepted: 25 November 1997     

Vibrational mode and collision energy effects on reaction of H2CO+ with CO2

The effects of collision energy (Ecol) and five different modes of H2CO+ vibration on the title reaction have been studied over the center-of-mass Ecol range from 0.1 to 3.2 eV, including measurements of product ion recoil velocity distributions. Electronic structure and Rice-Ramsperger-Kassel-Marcus calculations were used to examine properties of various complexes and transition states that might be important along the reaction coordinate. Two product channels are observed, corresponding to Hydrogen Transfer (HT) and Proton Transfer (PT). Both channels are endothermic with similar onset energies of approximately 0.9 eV; however, HT dominates over the entire Ecol range and accounts for 70-85% of the total reaction cross section. Both HT and PT occur by direct mechanisms over the entire Ecol range, and have similar dependence on reactant vibrational and collision energy. Despite these similarities, and the fact that the two channels are nearly isoenergetic and differ only in which product moiety carries the charge, their dynamics appear quite different. PT occurs primarily in large impact parameter stripping collisions, where most of the available energy is partitioned to product recoil. HT, in contrast, results in internally hot products with little recoil energy and a more forward-backward symmetric product velocity distribution. Vibration is found to affect the reaction differently in different collision energy regimes. The appearance thresholds are found to depend only on total energy, i.e., all modes of vibration are equivalent to Ecol. With increasing Ecol, vibrational energy becomes increasingly effective, relative to Ecol, at driving reaction. For HT, this transition occurs just above threshold, while for PT it begins at roughly twice the threshold energy.     

Direct rate measurements on the reactions N + OH → NO + H And O + OH → O2 + H

Rate constants for the radical-radical reactions N + OH → NO + H (1), and O + OH → O₂ + H (2) have been measured for the first time by a direct method. In each experiment, a known concentration of N or O atoms is established in a discharge-flow system. OH radicals are then created by flash photolysis of H₂O present in the flowing gas, and the disappearance of OH is monitored by time-resolved observations of its resonance fluorescence. The experiments yield K₁ = (5.0 = 1.2) × 10^?11 cm³ molecule^?1 s^?1 and k₂ = (3.8 = 0.9) × 10^?11 cm³ molecule^?1 s^?1, for the reactions at 298 = 5 K.