A quantum scattering study of collinear state-to-state reaction probabilities for the F+H_2(ν)→-HF(v'''')+H system

A new quantum scattering approach (linear combination of arrangement channels-scattering wavefunction,LCAC-SW) proposed by Deng and his co-workers is used to calculate collinear state-to-state reaction probabilities for the F + H-2(v)→HF(v')+H system.Several interesting problems such as threshold energy,compound states and enhance by translational energy of the reactants and the vibration excitation of products are discussed and they are compared with other theoretical investigations reported in the literature.It is shown that the LCAC-SW approach is the successful one of quantum scattering methods.     

Fully Λ-doublet resolved state-to-state differential cross-sections for the inelastic scattering of NO(X) with Ar

Fully Λ-doublet resolved state-to-state differential cross-sections (DCSs) for the collisions of the open-shell NO(X, (2)Π(1/2), ν = 0, j = 0.5) molecule with Ar at a collision energy of 530 cm(-1) are presented. Initial state selection of NO(X, (2)Π(1/2), j = 0.5, f) was performed using a hexapole so that the (low field seeking) parity of ε = -1, corresponding to the f component of the Λ-doublet, could be selected uniquely. Although the Λ-doublet levels lie very close in energy to one another and differ only in their relative parities, they exhibit strikingly different DCSs. Both spin-orbit conserving and spin-orbit changing collisions have been studied, and the previously unobserved structures in the fully quantum state-to-state resolved DCSs are shown to depend sensitively on the change in parity of the wavefunction of the NO molecule on collision. In all cases, the experimental data are shown to be in excellent agreement with rigorous quantum mechanical scattering calculations.     

Communication: state-to-state quantum dynamics study of the OH + CO → H + CO2 reaction in full dimensions (J = 0)

A full dimensional state-to-state quantum dynamics study is carried out for the prototypical complex-formation OH + CO → H + CO(2) reaction in the ground rovibrational initial state on the Lakin-Troya-Schatz-Harding potential energy surface by using the reactant-product decoupling method. With three heavy atoms and deep wells on the reaction path, the reaction represents a huge challenge for accurate quantum dynamics study. This state-to-state calculation is the first such a study on a four-atom reaction other than the H(2) + OH ? H(2)O + H and its isotope analogies. The product CO(2) vibrational and rotational state distributions, and product energy partitioning information are presented for ground initial rovibrational state with the total angular momentum J = 0.     

A transition state view on reactive scattering: initial state-selected reaction probabilities for the H + CH4 → H2 + CH3 reaction studied in full dimensionality

Initial state-selected reaction probabilities for the H+CH(4)→H(2)+CH(3) reaction are computed for vanishing total angular momentum by full-dimensional calculations employing the multiconfigurational time-dependent Hartree approach. An ensemble of wave packets completely describing reactivity for total energies up to 0.58 eV is constructed in the transition state region by diagonalization of the thermal flux operator. These wave packets are then propagated into the reactant asymptotic region to obtain the initial state-selected reaction probabilities. Reaction probabilities for reactants in all rotational states of the vibrational 1A(1), 1F(2), and 1E levels of methane are presented. Vibrational excitation is found to decrease reactivity when reaction probabilities at equivalent total energies are compared but to increase reaction probabilities when the comparison is done at the basis of equivalent collision energies. Only a fraction of the initial vibrational energy can be utilized to promote the reaction. The effect of rotational excitation on the reactivity differs depending on the initial vibrational state of methane. For the 1A(1) and 1F(2) vibrational states of methane, rotational excitation decreases the reaction probability even when comparing reaction probabilities at equivalent collision energies. In contrast, rotational energy is even more efficient than translational energy in increasing the reaction probability when the reaction starts from the 1E vibrational state of methane. All findings can be explained employing a transition state based interpretation of the reaction process.     

Toward the exact solution of the electronic Schrödinger equation for noncovalent molecular interactions: worldwide distributed quantum monte carlo calculations

Quantum Monte Carlo (QMC) calculations on the stacked (st) and Watson/Crick (wc) bound adenine/thymine (A/T) and cytosine/guanine (C/G) DNA base pair complexes were made possible with the first large scale distributed computing project in ab initio quantum chemistry, Quantum Monte Carlo at Home (QMC@HOME). The results for the interaction energies (wc-A/T = 15.7 kcal/mol, wc-C/G = 30.2 kcal/mol, st-A/T = 13.1 kcal/mol, st-C/G = 19.6 kcal/mol) are in very good agreement with the best known coupled-cluster based estimates. The accuracy of these values is further supported by calculations on the S22 benchmark set of noncovalently bound systems, for which we obtain a small mean absolute deviation of 0.68 kcal/mol. Our results support previous claims that the stacking energies are of comparable magnitude to the interactions of the commonly discussed hydrogen-bonded motif. Furthermore, we show that QMC can serve as an advantageous alternative to conventional wave function methods for large noncovalently bound systems. We also investigated in detail all technical parameters of the QMC simulations and recommend a careful optimization procedure of the Jastrow correlation factors in order to obtain numerically stable and reliable results.     

Approximate analytical solutions for arbitrary l-state of the Hulthén potential with an improved approximation of the centrifugal term

An approximate analytical solution of the radial Schr?dinger equation for the generalized Hulthén potential is obtained by applying an improved approximation of the centrifugal term. The bound state energy eigenvalues and the normalized eigenfunctions are given in terms of hypergeometric polynomials. The results for arbitrary quantum numbers n _r and l with different values of the screening parameter δ are compared with those obtained by the numerical method, asymptotic iteration, the Nikiforov-Uvarov method, the exact quantization rule, and variational methods. The results obtained by the method proposed in this work are in a good agreement with those obtained by other approximate methods.      

The variational iteration method for solving the Volterra integro-differential forms of the Lane–Emden equations of the first and the second kind

In this paper, we establish the Volterra integro-differential forms of the Lane–Emden equations. We use the variational iteration method (VIM) to effectively treat these forms. The Volterra integro-differential forms of the Lane–Emden equations overcome the singular behavior at the origin $x=0$ and do not use a variety of Lagrange multipliers. Several numerical examples are examined to show the validity of the integro-differential forms.     

Mechanism of a chemical classic: quantum chemical investigation of the autocatalyzed reaction of the serendipitous wöhler synthesis of urea

The detailed reaction pathways for the ammonium cyanate transformation into urea (W?hler's reaction) in the gas phase, in solution, and in the solid state have exhaustively been explored by means of first-principles quantum chemical calculations at the B3LYP level of theory using the 6-31G(d,p) basis set. This serendipitous synthesis of urea is predicted to proceed in two steps; the first step involves the decomposition of the ammonium cyanate to ammonia and isocyanic or cyanic acid, and the second one, which is the main reaction step (and probably the rate-determining step), involves the interaction of NH(3) with either isocyanic or cyanic acid. Several alternative pathways were envisaged for the main reaction step of W?hler's reaction in a vacuum involving the formation of "four-center" transition states. Modeling W?hler's reaction in aqueous solution and in the solid state, it was found that the addition of NH(3) to both acids is assisted (autocatalyzed) by the active participation of extra H(2)O and/or NH(3) molecules, through a preassociative, cooperative, and hydrogen-transfer relay mechanism involving the formation of "six-center" or even "eight-center" transition states. The most energetically economic path of the rate-determining step of W?hler's reaction is that of the addition of NH(3) to the C=N double bond of isocyanic acid, directly affording urea. An alternative pathway corresponding to the anti-addition of ammonia to the Ctbd1;N triple bond of cyanic acid, yielding urea's tautomer HN=C(OH)NH(2), seems to be another possibility. In the last case, urea is formed through a prototropic tautomerization of its enolic form. The energies of the reactants, products, and all intermediates along with the barrier heights for each reaction path have been calculated at the B3LYP/6-31G(d,p) level of theory. The geometry optimization and characterization of all of the stationary points found on the potential energy hypersurfaces was performed at the same level of theory.     

An ab initio-based global potential energy surface for the SH3 system and full-dimensional state-to-state quantum dynamics study for the H2 + HS → H2S + H reaction

An accurate potential energy surface for the ground electronic state of SH₃ system has been constructed with 41,882 high level ab initio energy points and the neural network fitting method. The time-dependent wave packet method has been used to calculate the first state-to-state differential cross sections for the title reaction up to 1.2 eV in full dimensions, based on the reactant–product decoupling scheme. It is found that the majority of H₂S are produced in the ground vibrational state, with a large fraction of available energy for the reaction ending up as product translational motion. The differential cross sections at the threshold energy are dominated by a very narrow peak in the backward direction. With the increase of collision energy, the width of the angular distribution increases considerably, which is a typical feature of a direct reaction via abstract mechanism, similar to the H₂ + OH → H₂O + H reaction. © 2018 Wiley Periodicals, Inc.     

Accurate quantum wave packet calculations for the F + HCl → Cl + HF reaction on the ground 1(2)A' potential energy surface

We present converged exact quantum wave packet calculations of reaction probabilities, integral cross sections, and thermal rate coefficients for the title reaction. Calculations have been carried out on the ground 1(2)A' global adiabatic potential energy surface of Deskevich et al. [J. Chem. Phys. 124, 224303 (2006)]. Converged wave packet reaction probabilities at selected values of the total angular momentum up to a partial wave of J = 140 with the HCl reagent initially selected in the v = 0, j = 0-16 rovibrational states have been obtained for the collision energy range from threshold up to 0.8 eV. The present calculations confirm an important enhancement of reactivity with rotational excitation of the HCl molecule. First, accurate integral cross sections and rate constants have been calculated and compared with the available experimental data.     

Low temperature rate constants for the N + CN → N(2) + C reaction: two-dimensional quantum capture calculations on an accurate potential energy surface

The title reaction is thought to be responsible for the production of molecular nitrogen in interstellar clouds. In this work, we report quantum capture calculations on a new two-dimensional potential energy surface determined by interpolating high-level ab initio data. The low-temperature rate constant calculated using a capture model is quite large and has a positive temperature dependence, in agreement with a recent experiment. The origin of the aforementioned behaviors of the rate constant is analyzed.     

The transition probabilities from the ground state to the excited J = 0 1Σu(+) levels of H2: measurements and ab initio quantum defect study

The energies, widths and absolute intensities of the P(1) v' = 0, J' = 1 absorption transitions of H(2) have been measured in the spectral range of 81-75 nm using monochromatized synchrotron radiation. This work completes and extends previous observations, in particular those of Herzberg and Jungen [J. Mol. Spectrosc. 41, 425 (1972)]. Ab initio multichannel quantum defect theory (MQDT) is used to corroborate the spectral analysis of the experimental data. Line intensities and decay widths are also calculated using MQDT.     

Julia–Kocienski olefination: a key reaction for the synthesis of macrolides

The unification of carbonyl compounds and heteroaryl sulfones provides one of the best methods for the construction of C–C double bond for synthetic chemists in designing synthetic routes to natural and non-natural products. For the C–C double bond formation, olefination, particularly the Julia–Kocienski olefination (JK-olefination) has emerged as a powerful key reaction in the synthesis of natural products that contain macrocycles. Molecules of interest include macrolides, whose biological importance, lack of natural resources, and interesting structure placed a challenge among the scientific community for their total synthesis. Thus, for systematic documentation we have summarized the synthetic approaches toward several important macrolides highlighting the Julia–Kocienski olefination as one of the key steps. This review is intended to show the utility of the Julia–Kocienski olefination in the synthesis of biologically important macrocyclic natural products.     

Kinetics of the reaction of the heaviest hydrogen atom with H2, the 4Heμ + H2 → 4HeμH + H reaction: experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass

The neutral muonic helium atom (4)Heμ, in which one of the electrons of He is replaced by a negative muon, may be effectively regarded as the heaviest isotope of the hydrogen atom, with a mass of 4.115 amu. We report details of the first muon spin rotation (μSR) measurements of the chemical reaction rate constant of (4)Heμ with molecular hydrogen, (4)Heμ + H(2) → (4)HeμH + H, at temperatures of 295.5, 405, and 500 K, as well as a μSR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, k(Heμ), are compared with the predictions of accurate quantum mechanical (QM) dynamics calculations carried out on a well converged Born-Huang (BH) potential energy surface, based on complete configuration interaction calculations and including a Born-Oppenheimer diagonal correction. At the two highest measured temperatures the agreement between the quantum theory and experiment is good to excellent, well within experimental uncertainties that include an estimate of possible systematic error, but at 295.5 K the quantum calculations for k(Heμ) are below the experimental value by 2.1 times the experimental uncertainty estimates. Possible reasons for this discrepancy are discussed. Variational transition state theory calculations with multidimensional tunneling have also been carried out for k(Heμ) on the BH surface, and they agree with the accurate QM rate constants to within 30% over a wider temperature range of 200-1000 K. Comparisons between theory and experiment are also presented for the rate constants for both the D + H(2) and Mu + H(2) reactions in a novel study of kinetic isotope effects for the H + H(2) reactions over a factor of 36.1 in isotopic mass of the atomic reactant.     

What are the most efficient basis set strategies for correlated wave function calculations of reaction energies and barrier heights?

As electronic structure methods are being used to obtain quantitatively accurate reaction energies and barrier heights for increasingly larger systems, the choice of an efficient basis set is becoming more critical. The optimum strategy for achieving basis set convergence can depend on the way that electron correlation is treated and can take advantage of flexibility in the order in which basis functions are added. Here we study several approaches for estimating accurate reaction energies and barrier heights from post-Hartree-Fock electronic structure calculations. First and second, we evaluate methods of estimating the basis set limit of second order Mo?ller-Plesset perturbation theory and of coupled cluster theory with single and double excitations and a quasiperturbative treatment of connected triple excitations by using explicitly correlated basis functions (in the F12a implementation) along with valence, polarization, and diffuse one-electron basis functions. Third, we test the scheme of adding a higher-order correction to MP2 results (sometimes called MP2∕CBS + ΔCCSD(T)). Finally, we evaluate the basis set requirements of these methods in light of comparisons to Weizmann-3.2, Weizmann-4, and CCSDT(2)(Q)∕CBS+CV+R results.     

Exact quantum scattering calculation of transport properties for free radicals: OH(X(2)Π)-helium

Transport properties for OH-He are computed through quantum scattering calculations using the ab initio potential energy surfaces determined by Lee et al. [J. Chem. Phys. 113, 5736 (2000)]. To gauge the importance of the open-shell character of OH and the anisotropy of the potential on the transport properties, including the collision integrals Ω((1,1)) and Ω((2,2)), as well as the diffusion coefficient, calculations were performed with the full potential, with the difference potential V(dif) set to zero, and with only the spherical average of the potential. Slight differences (3%-5%) in the computed diffusion coefficient were found between the values obtained using the full potential and the truncated potentials. The computed diffusion coefficients were compared to recent experimental measurements and those computed with a Lennard-Jones (LJ) 12-6 potential. The values obtained with the full potential were slightly higher than the experimental values. The LJ 12-6 potential was found to underestimate the variation in temperature as compared to that obtained using the full OH-He ab initio potential.     

Higher-order split operator schemes for solving the Schrödinger equation in the time-dependent wave packet method: applications to triatomic reactive scattering calculations

The efficiency of the numerical propagators for solving the time-dependent Schr?dinger equation in the wave packet approach to reactive scattering is of vital importance. In this Perspective, we first briefly review the propagators used in quantum reactive scattering calculations and their applications to triatomic reactions. Then we present a detailed comparison of about thirty higher-order split operator propagators for solving the Schr?dinger equation with their applications to the wave packet evolution within a one-dimensional Morse potential, and the total reaction probability calculations for the H + HD, H + NH, H + O(2), and F + HD reactions. These four triatomic reactions have quite different dynamic characteristics and thus provide a comprehensive picture of the relative advantages of these higher-order propagation methods for describing reactive scattering dynamics. Our calculations reveal that the most often used second-order split operator method is typically more efficient for a direct reaction, particularly for those involving flat potential energy surfaces. However, the optimal higher-order split operator methods are more suitable for a reaction with resonances and intermediate complexes or a reaction experiencing potential energy surface with fluctuations of considerable amplitude. Three 4th-order and one 6th-order split operator methods, which are most efficient for solving reactive scattering in various conditions among the tested ones, are recommended for general applications. In addition, a brief discussion on the relative performance between the Chebyshev real wave packet method and the split operator method is given. The results in this Perspective are expected to stimulate more applications of (high-order) split operators to the quantum reactive scattering calculation and other related problems.     

The reaction mechanism for the organocatalytic ring-opening polymerization of l-lactide using a guanidine-based catalyst: hydrogen-bonded or covalently bound?

We have investigated two alternative mechanisms for the ring-opening polymerization of l-lactide using a guanidine-based catalyst, the first involving acetyl transfer to the catalyst, and the second involving only hydrogen bonding to the catalyst. Using computational chemistry methods, we show that the hydrogen bonding pathway is considerably preferred over the acetyl transfer pathway and that this is consistent with experimental information.