High-level ab initio calculations on CH+2(2A1) + PO(2II) reactions

We present ab initio calculations carried out in the framework of the G 2 theory on the singlet and triplet potential energy surfaces corresponding to the gas-phase between CH⁺₂ and PO. The global minimum of both potential energy surfaces is a cyclic singlet-state cation. Oxygen attachment of PO to CH⁺₂ in a triplet configuration is accompanied by a P(SINGLEBOND)O bond fission, with the result that the corresponding global minimum is an ion-dipole complex between P⁺(³P) and formaldehyde. This is also consistent with the fact that our results predict the formation of formaldehyde to be highly exothermic, either as a neutral or as radical cation. Both charge-transfer processes yielding CH₂(³B₁) or CH₂(¹A₁) are also exothermic. The formation of other carbon and oxygen containing species are endothermic. © 1996 John Wiley & Sons, Inc.     

Comparison of quantum, classical, and ring-polymer molecular dynamics infra-red spectra of Cl(H2O) and H(H2O)2

We present a comparison of the infra-red spectra of Cl⁻(H₂O) and H⁺(H₂O)₂ obtained with classical and ring-polymer molecular dynamics with previous quantum calculations. Full-dimensional ab initio-based potential and dipole-moment surfaces are used in these calculations.     

Quantum and quasiclassical study of the collinear reaction O(3P) + H2 → OH + H using a LEPS and fitted AB initio potential energy surface

Accurate quantum calculations of reaction probabilities P^T_ν′←ν have been carried out for the collinear reaction O(³P) + H₂ (ν = 0,1) → OH(ν′) + H using a LEPS and fitted ab initio potential energy surface. The energy dependence of the P^T_{ν′ ← ν} is similar for both surfaces. Collinear quasiclassical trajectory calculations have also been carried out, for comparison, on the LEPS surface for ν = 0, 1 and 2.     

High‐Temperature Rate Constants for H + Tetramethylsilane and H + Silane and Implications about Structure–Activity Relationships for Silanes

The shock‐tube technique has been used to investigate the reactions H + SiH₄ → H₂ + SiH₃ (R1) and H + Si(CH₃)₄ → Si(CH₃)₃CH₂ + H₂ (R2) behind reflected shock waves. C₂H₅I was used as a thermal in situ source for H atoms. For reaction (R1), the experiments covered a temperature range of 1170–1251 K and for (R2) 1227–1320 K. In both cases, the pressures were near 1.5 bar. In these experiments, H atoms were monitored with atomic resonance absorption spectrometry. Fits to the H‐atom temporal concentration profiles applying postulated chemical kinetic reaction mechanisms were used for determining the rate constants k₁ and k₂. Experimental rate constants were well represented by the Arrhenius equations k₁(T) = 2.75 × 10⁻⁹ exp(−37.78 kJ mol⁻¹/RT) cm³ s⁻¹ and k₂(T) = 1.17 × 10⁻⁷ exp(−86.82 kJ mol⁻¹/RT) cm³ s⁻¹. Transition state theory (TST) calculations based on CBS‐QB3 and G4 levels of theory show good agreement with experimentally obtained rate constants; the experimental values for k₁ and k₂ are ∼40% lower and ∼50% larger than theoretical predictions, respectively. For the development of a mechanism describing the thermal decomposition of tetramethylsilane (Si(CH₃)₄; TMS), also TST‐based rate constants for reaction CH₃ + Si(CH₃)₄ → Si(CH₃)₃CH₂ + CH₄ (R3) were calculated. A comparison between experimental and theoretical rate constants k₂ and k₃ with available rate constants from the literature indicates that Si(CH₃)₄ has very similar reactivity toward H abstractions like neopentane (C(CH₃)₄), which is the analog hydrocarbon to TMS. Based on these results, the possibility of drawing reactivity analogies between hydrocarbons and structurally similar silicon‐organic compounds for H‐atom abstractions is discussed.     

Rates of reaction of atomic oxygen with C2H3F,C2H3Cl,C2H3Br, 1,1-C2H2F2, and 1,2-C2H2F2

Rate constants for the reactions of atomic oxygen (O³P) with C₂H₃F, C₂H₃Cl, C₂H₃Br, 1,1-C₂H₂F₂, and 1,2-C₂H₂F₂ have been measured at 307°K using a discharge-flow system coupled to a mass spectrometer. The rate constants for these reactions are (in units of 10¹¹ cm³ mole^?1 s^?1) 2.63 ± 0.38, 5.22 ± 0.24, 4.90 ± 0.34, 2.19 ± 0.18, and 2.70 ± 0.34, respectively. For some of these reactions, the product carbonyl halides were identified.     

A coupled states calculation of accurate quantum rate constants for H + H2

In this article we present the results of converged quantum reactivescattering calculations of thermal rate constants for H + H₂ using the Liu-Siegbahn-Truhlar-Horowitz (LSTH) potential energy surface. These calculations are based on the coupled states (CS) approximation wherein rotational states having different body fixed angular momentum projection quantum numbers are decoupled. By comparision with accurate coupled channel results on the Porter-Karplus No. 2 (PK2) potential surface, we estimate that the maximumerror in thermal rate constants arising from both this approximation and from other numerical approximations in the calculation is less than 25%. We also show that the sum over projection quantum numbers Ω associated with the CS calculation may be approximated quite accurately in terms of the Ω = 0 rate constants by assuming that the |Ω| > 0 rate constants differ from Ω = 0 by a shift in activation energy, which reflects the vibrationally adiabatic bending energy associated with each Ω. Comparison of the LSTH rate constants with experiment indicates average errors of 16% and 24% relative to the two modern measurementsof the rate constants for H + H₂. These errors are reduced to 18% and 9% if the CS rate constants are multiplied by exp(0.0065 eV/kT). The expected error (based on recent quantum structure calculations) associated with the 0.425 eV barrier of theLSTH potential surface is 0.0065 eV. Overall, the agreement of either the LSTH or modified LSTH rate constants with experiment is within the 32% maximum disagreement between the two experimental measurements at all butthe lowest temperature that has been studied. Comparison of our CS rate constants with the results from simpler theories is considered using both the LSTH and PK2 potential surfaces. The best overall agreement is with transition state theories that use accurate dynamical methods to calculate tunnelling factors. These include reduced dimensionality quantum dynamics methods and variational transition state theory using either the Marcus-Coltrin or least action ground-state tunnelling paths. Comparison with the results of quasiclassical trajectory calculations indicates substantial errors at low temperatures.     

Theoretical rate constant calculations for O(3P) with saturated hydrocarbons

Theoretical rate constants have been calculated for O(³P) with five saturated hydrocarbons, CH₄, C₂H₆, C₃H₈, iso-C₄H₁₀, and neo-C₅H₁₂. The method of choice is bond energy–bond order (BEBO) with activated complex theory (ACT). Because the BEBO method is empirical, O(³P) + CH₄ is evaluated first, and the theoretical results are compared to more rigorous calculations and to the empirical transition state method. Comparisons are also made between predictions and experimental results. All of these comparisons show that the BEBO-ACT method gives results which are consistent with experiment and other theory. Because the method is successful, the other four cases are then considered. Ambiguity arises for the higher hydrocarbons from the problem of internal rotations in the activated complexes, and three cases are evaluated. Best agreement with experiment is obtained if the primary rotor(s) in the complexes are considered to be free. Predictions of rate constants are made from 500 to 2500 K. Throughout the discussion issues of theory which are common to any ACT calculation from any method of potential energy evaluation (LEP, LEPS, or ab initio quantum mechanics) are featured.     

Ab initio study,including electron correlation,of the electronic structures,the dipole moments,the static polarizabilities and of the harmonic force fields of H2CO,H2CS and H2SiO

Ab initio calculations including electron correlation (on the PNO-CI and CEPA-PNO levels) are carried out for the isovalence electronic molecules H₂CO, H₂CS and H₂SiO, and for comparison also for H₂O and CO. The CEPA equilibrium distances are accurate to within 0.003 Å, while SCF results show significantly larger errors. The harmonic force constants on CEPA level are satisfactory as well, but for stretching of double or triple bonds inclusion of singly substituted configurations is imperative. Dipole moments were obtained with an error of 0.1 Debye from CEPA calculations with sufficiently large basis sets and inclusion of singly substituted configurations. The dipole polarizabilities are less sensitive to correlation effects but require larger basis sets.The population analysis reveals that the SiO bond in H₂SiO is highly polar and thatd-AO's cannot be regarded as valence AO's in any of the molecules of this study. The binding energy of H₂SiO (with respect to H₂Si(¹ A ₁) + O(³ P)) is predicted as 140 ± 5 kcal/mol. The contributions of different pairs in terms of localized orbitals to the correlation energy of the molecules of this study are analyzed.     

Gas phase reactions of the ion C5H5Fe+: A kinetic study

The kinetics of gas phase reactions of the ion C₅H₅Fe⁺ with oxygen (Me₂CO, Me₂O, MeOH, iso-propanol, H₂O) and nitrogen (NH₃, NH₂Me, NHMe₂, NMe₃) donor ligands have been studied by ion trap mass spectrometry. While in the literature reactions of the ion Fe⁺, with the same ligands, the principal reaction path involves fragmentation in almost all the reactions of the ion C₅H₅Fe⁺, formation of adduct ions is the major reaction path. The reactivity of these two ions is briefly compared in the ion trap conditions. Kinetic data for the ion C₅H₅Fe⁺ indicate that the reactions show a large range of efficiency and a linear correlation is found between the log of the reaction rate constants and the ionization energy of ligands with the same donor atom.     

Kinetics and mechanisms for reactions of HNO with CH3 and C6H5 studied by quantum‐chemical and statistical‐theory calculations

Kinetics and mechanisms for the reactions of HNO with CH₃ and C₆H₅ have been investigated by ab initio molecular orbital (MO) and transition‐state theory (TST) and/or Rice‐Ramsperger‐Kassel‐Marcus/Master Equation (RRKM/ME) calculations. The G2M(RCC, MP2)//B3LYP/6‐31G(d) method was employed to evaluate the energetics for construction of their potential energy surfaces and prediction of reaction rate constants. The reactions R + HNO (R = CH₃ and C₆H₅) were found to proceed by two key product channels giving (1) RH + NO and (2) RNO + H, primarily by direct abstraction and indirect association/decomposition mechanisms, respectively. As both reactions initially occur barrierlessly, their rate constants were evaluated with a canonical variational approach in our TST and RRKM/ME calculations. For practical applications, the rate constants evaluated for the atmospheric‐pressure condition are represented by modified Arrhenius equations in units of cm³ mol^?1 s^?1 for the temperature range 298–2500 K: κ_1A = 1.47 × 10¹¹ T ^0.76 exp[?175/ T ], κ_2A = 8.06 × 10³ T ^2.40 exp[?3100/ T ], κ_1B = 3.78 × 10⁵ T ^2.28 exp[230/ T ], and κ_2B = 3.79 × 10⁹ T ^1.19 exp[?4800/ T ], where A and B represent CH₃ and C₆H₅ reactions, respectively. Based on the predicted rate constant at 1 atm pressure for R + HNO → RNO + H, we estimated their reverse rate constants for R + HNO production from H + RNO in units of cm³ mol^?1 s^?1: κ_?2A′ = 7.01 × 10¹⁰ T ^0.84 exp[120/ T ] and κ_?2B′ = 2.22 × 10¹⁹ T ^?1.01 exp[?9700/ T ]. The heats of formation at 0 K for CH₃NO, CH₃N(H)O, CH₃NOH, C₆H₅N(H)O, and C₆H₅NOH have been estimated to be 18.6, 18.1, 22.5, 47.2, and 50.7 kcal mol^?1 with an estimated ±1 kcal mol^?1 error. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 261–274, 2005     

Theoretical study of the reaction Ne + H+2 → NEH+ + H in the 2A′ ground state

A three-dimensional potential energy surface for the ²A′ ground state of the system (Ne? H₂)⁺ (²Σ⁺ in collinear geometry) has been calculated at SCF and CEPA levels. This surface describes the abstraction reaction which is endoergic by 0.57 eV (ΔH⁰₀) and has been studied recently by different experimental groups at low collision energies. Our CEPA calculations yield an endoergicity of 0.55 eV (ΔH⁰₀). The ²A′ surface has a minimum at collinear geometry with R_Ne—H = 2.29 a₀ and R_{H? H} = 2.08 a₀ and a well depth of 0.49 eV relative to Ne + H⁺₂. The effects of electron correlation on the shape of the surface and on the well depth are discussed. An analytic fit of the collinear part of the surface has been constructed based on Simon's proposal of using polynomials in the coordinates (R? R_e)/R instead of (R? R_e). The fitted potential is used for quantum mechanical scattering calculations with the finite element method (FEM ). Preliminary results for reaction probabilities for H⁺₂ in different vibrationally excited states are given and compared to the experimental results.     

Calculation of the Gibbs Energy of the Reaction OH-·(H2O)n-1 + H2O = OH-·(H2O)n by the Monte-Carlo Method

The energy, the Gibbs energy of the reaction OH^-·(H₂O) _{n- 1} + H₂O = OH^-·(H₂O) _n are calculated by the Monte-Carlo method with a large canonical ensemble for n = 1, ..., 20. The ion-waternonpair interaction potential was obtained by numerical fitting of calculated Gibbs energy and entropy of (H₂O)_n clusters (n = 1, ..., 5) to experimental ones. A good fit to experiment both of the internal energy and the Gibbs energy can be obtained in terms of a model allowing for nonpair interaction. It is shown that constructing an ion-water interaction potential without allowance for the entropy factor can lead to considerable errors in the Gibbs energy of cluster formation and in the nucleation rate.     

AM1 studies on the potential energy surface for the proton transfer in protonated water clusters,H+(H2O)n

The potential energy surfaces for the proton transfer processes in H⁺(H₂O)_n with n=2 ～ 11 have been studied using the semiempirical AM1 method. Two model systems were adopted: branched and linear systems. The branched system showed a tendency to form a bulk cluster, while the linear system showed a tendency toward a constant barrier height with increasing number of water molecules in the model system. The potential energy surfaces were discussed using Marcus theory. In the case of H⁺ (H₂O)_n with n=10 and 11, the intrinsic barrier to the proton transfer was found to be around 1.0 kcal/mol.     

An Ab initio determination of the rate constant for H2 + CN → H + HCN

The reactants, products, and saddle point for the reaction H₂ + CN → H + HCN have been studied by ab initio calculations. The computed structures, frequencies, and energetics are compared directly to available measurements and, indirectly, to experimental rateconstants. The theoretical rate constants used in the comparison are calculated with conventional transition state theory. By reduction of the computed reaction barrier to 4.1 kcal mol,^?1 good agreement with experimental rate constants is obtained over a 3250-K temperature range. This computed rate constant is well represented by the form 4.9 × 10_?18 T^2.45 e^{?1, 126/T} over the temperature range of 250 K–3500 K. Substantial reaction rate curvature is found due to low-frequency bending modes at the saddle point. The results for this reaction are compared to other abstraction reactions involving H atom transfer to identify correlations between reaction exothermicity and both abstraction barriers and reaction rate curvature.     

Stationary points on the potential energy surface of O2−HF and O2−H2O

The determination of minima and saddle points on the potential energy surfaces of the hydrogen bonded species O₂^?HF and O₂^?H₂O is performed with unrestricted Hartree-Fock calculations. Geometries, electron density distributions, and relative energies for every stationary point are reported. Only one true minimum is found for O₂^?HF and for O₂^?H₂O, and this approximately corresponds to a structure where the partially positive hydrogen atom is located along one of the superoxide ion electron lone-pair directions. Calculated ΔH, ΔS, and ΔG values for the reaction between O₂^? and H₂O are in good agreement with experimental data.     

Semiclassical variational transition state calculations for the reactions of H and D with thermal and vibrationally excited H2

We present calculations of the rate constants for the title reactions on a new accurate potential energy surface with a 9.65 kcal mol^?1 barrier and a carefully fitted long-range attraction. The low-temperature thermal rate constant decreases from the previously calculated value, corresponding to a surface with a barrier of 9.80 kcal mol^?1, which is opposite to the direction of change expectedbecause of the change in barrier height. This demonstrates the sensitivity of tunneling contributions to more global characteristics of the surface. The excited-state (n = 1) rate constants alsochange slightly, but not nearly enough to settle the controversial disagreement of theory with experiment for these rate constants.     

Pathways of the reactions of nucleophilic addition of H2O and HF molecules to formaldehyde in the gas phase and in the complex with formic acid:ab initio calculations

The gradient pathways of the reactions of nucleophilic addition of H₂O and HF molecules to formaldehyde in the gas phase and in the XH…H₂CO…HC(O)OH complex (X=OH, F) were calculated by theab initio RHF/6-31G^**, MP2(fc)/6-31G^**, and MP2(full)/6-311++G^** methods. Both reactions proceed concertedly. The formation of H-bonded bimolecular pre-reaction complexes is the initial stage of the gas-phase reactions; at the same time, no indications of the formation of stable π-complexes were found on the potential energy surfaces of systems under study. The calculated energy barriers to the gasphase reactions exceed 40 kcal mol⁻¹, while those to reactions in the complex XH…H₂CO…HC(O)OH (X=OH, F) become more than halved. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2146–2154, November, 1998.     

Isotope effect in Ni + C2H4 (C2D4) association reaction

The association reactions of atomic nickel with ethene and fully deuterated ethene in carbon dioxide buffer gas at 295 K have been investigated in the pressure range 5–100 torr, using a laser photolysis-laser fluorescence technique. By comparison with results of ab initio quantum chemistry calculations for the complex Ni[C₂H₄], the data are shown to be consistent with reaction on both ground and excited state potential energy surfaces. A simple rate equations treatment is described which shows the form of the pressure dependence of the second-order recombination rate coefficient in this case. Under conditions which are expected to hold for the Ni + C₂H₄ (C₂D₄) reaction, the pressure dependence has the standard Lindemann-Hinshelwood form, with the limiting high pressure rate constant given by an apparent value which reflects the degree to which the participating electronic states are coupled by nonadiabatic transitions. The limiting high pressure behavior of the recombination rate coefficient for Ni + C₂H₄ is not strongly affected by deuterium isotope substitution. However, the effect on the low pressure rate constant is large and consistent with RRKM unimolecular reaction theory. This validates the use of RRKM calculations for estimating the binding energy of the complex from kinetic data. The binding energy of Ni[C₂H₄] is estimated to be 35.2 ± 4.2 kcal mol^?1. © 1994 John Wiley & Sons, Inc.     

Mixed chromium(III) complexes with pyridinedicarboxylato and oxalato ligands: kinetic studies in HClO<Subscript>4</Subscript> solutions

Three chromium(III) complexes of general formula [Cr(ox)₂(pdaH)]²⁻ (where ox = C₂O₄ ²⁻ and pdaH⁻ is N,O-bonded 2,3-, 2,4- or 2,5-pyridinedicarboxylic acid anion) were obtained and characterized in solution. Acid-catalysed aquation of [Cr(ox)₂(pdaH)]²⁻ gave two products: [Cr(ox)(pdaH)(H₂O)₂]⁰ (P₁) and cis-[Cr(ox)₂(H₂O)₂]²⁻ (P₂). The kinetics of these reactions were studied spectrophotometrically, within the 0.1–1.0 M HClO₄ range, and the pseudo-first-order rate constants for the oxalato (k _obs1) and pdaH⁻ (k _obs2) ligands dissociation were calculated based on the determined pseudo-first-order rate constants (k _obs) and P₁:P₂ molar ratio. The dependencies of the pseudo-first-order rate constants on [H⁺] are as follows: k _obs1 = b ₁[H⁺] and k _obs2 = b ₂[H⁺], where b ₁ and b ₂ are the second-order rate constants for the oxalato and pdaH⁻ ligands dissociation, respectively. Kinetic parameters were determined and the mechanism of the pdaH⁻ ligand dissociation is proposed.     

FN+Cl Ions from Ionized F2NCl: a Computational Investigation on the Structure and Reactivity toward H2O

We have used various ab initio methods and basis sets to ascertain that the FN⁺Cl cation has a singlet ground state, ¹A′, which is more stable than the triplet state ³A″ by ca. 30 kcal mol^?1. We have subsequently used the Gaussian‐3 (G3) theory to explore the potential‐energy profile for the reaction between singlet FN⁺Cl and H₂O. The process commences by the effortless formation of a FN⁺Cl/H₂O complex, which, in principle, can undergo several alternative processes, including isomerization to N‐protonated FN(Cl)OH, 1,2‐elimination of HX (X=F or Cl), and 1,1‐loss of H₂. However, the energy barriers of all these processes are invariably larger than the energy (+18.1 kcal mol^?1) required for the formation of FN⁺Cl/H₂O from FN⁺Cl and H₂O, thus suggesting that, under gas‐phase thermal conditions, FN⁺Cl should be essentially unreactive toward H₂O. Comparing these theoretical findings with those concerning the reaction between FN⁺H, ClN⁺H, F₂N⁺, and H₂O, the reactivity order FN⁺H>F₂N⁺>ClN⁺H>FN⁺Cl, was derived, which parallels the trend we recently found by G2MS calculations concerning the Lewis acidity of these ions. This suggests the conceivable occurrence of correlations between the reactivity and thermochemical properties of these simple halonitrenium ions.