Theoretical analysis of photoinduced H-atom elimination in thiophenol

The photoinduced hydrogen elimination reaction in thiophenol via the conical intersections of the dissociative (1)pi sigma* excited state with the bound (1)pi pi* excited state and the electronic ground state has been investigated with ab initio electronic-structure calculations and time-dependent quantum wave-packet calculations. A screening of the coupling constants of the symmetry-allowed coupling modes at the (1)pi pi*-(1)pi sigma* and (1)pi sigma*-S-0 conical intersection shows that the SH torsional mode is by far the most important coupling mode at both conical intersections. A model including three intersecting potential-energy surfaces (S-0, (1)pi pi*, (1)pi sigma*) and two nuclear degrees of freedom (SH stretch and SH torsion) has been constructed on the basis of ab initio complete-active-space self-consistent field and multireference second-order perturbation theory calculations. The nonadiabatic quantum wave-packet dynamics initiated by optical excitation of the (1)pi pi* and (1)pi sigma* states has been explored for this three-state two-coordinate model. The photodissociation dynamics is characterized in terms of snapshots of time-dependent wave packets, time-dependent electronic population probabilities, and the branching ratio of the (2)sigma/(2)pi electronic states of the thiophenoxyl radical. The dependence of the timescale of the photodissociation process and the branching ratio on the initial excitation of the SH stretching and SH torsional vibrations has been analyzed. It is shown that the node structure, which is imposed on the nuclear wave packets by the initial vibrational preparation as well as by the transitions through the conical intersections, has a profound effect on the photodissociation dynamics. The effect of additional weak coupling modes of CC twist (nu(16a)) and ring-distortion (nu(16b)) character has been investigated with three-dimensional and four-dimensional time-dependent wave-packet calculations, and has been found to be minor. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4709608]

Thermal Decomposition of Propargyl Alcohol: Single Pulse Shock Tube Experimental and ab Initio Theoretical Study

Thermal decomposition of propargyl alcohol (C3H3OH), a molecule of interest in interstellar chemistry and combustion, was investigated using a single pulse shock tube in the temperature ranging from 953 to 1262 K. The products identified include acetylene, propyne, vinylacetylene, propynal, propenal, and benzene. The experimentally observed overall rate constant for thermal decomposition of propargyl alcohol was found to be k = 10((10.17 +/- 0.36)) exp(-39.70 +/- 1.83)/RT) s(-1) Ab initio theoretical calculations were carried out to understand the potential energy surfaces involved in the primary and secondary steps of propargyl alcohol thermal decomposition. Transition state theory was used to predict the rate constants, which were then used and refined in a kinetic simulation of the product profile. The first step in the decomposition is C-O bond dissociation, leading to the formation of two important radicals in combustion, OH and propargyl. This has been used to study the reverse OH propargyl radical reaction, about which there appears to be no prior work. Depending on the site of attack, this reaction leads to propargyl alcohol or propenal, one of the major products at temperatures below 1200 K. A detailed mechanism has been derived to explain all the observed products.

Study of structures, energies and vibrational frequencies of (O-2)(n)(+) (n=2-5) clusters by GGA and meta-GGA density functional methods

Using Generalized Gradient Approximation (GGA) and meta-GGA density functional methods, structures, binding energies and harmonic vibrational frequencies for the clusters O-4(+), O-6(+), O-8(+) and O-10(+) have been calculated. The stable structures of O-4(+), O-6(+), O-8(+) and O-10(+) have point groups D-2h, D-3h, D-4h, and D-5h optimized on the quartet, sextet, octet and dectet potential energy surfaces, respectively. Rectangular (D-2h) O-4(+) has been found to be more stable compared to trans-planar (C-2h) on the quartet potential energy surface. Cyclic structure (D-3h) of CA cluster ion has been calculated to be more stable than other structures. Binding energy (B.E.) of the cyclic O-6(+) is in good agreement with experimental measurement. The zero-point corrected B.E. of O-8(+) with D4h symmetry on the octet potential energy surface and zero-point corrected B.E. of O-10(+) with D-5h symmetry on the dectet potential energy surface are also in good agreement with experimental values. The B.E. value for O-4(+) is close to the experimental value when single point energy is calculated by Brueckner coupled-cluster method, BD(T). (C) 2014 Elsevier B.V. All rights reserved.

Microwave Spectrum of Hexafluoroisopropanol and Torsional Behavior of Molecules with a CF3-C-CF3 Group

This paper presents the first microwave spectroscopic investigation on hexafluoroisopropanol (HFIP). A pulsed nozzle Fourier transform microwave spectrometer has been used to determine the rotational constants for HFIP as A = 2105.12166(18) MHz, B = 1053.99503(12) MHz, and C = 932.33959(13) MHz. In addition, five isotopologues of HFIP have been observed experimentally to determine the accurate structure of HFIP. The observed spectrum could be assigned to the most stable conformer of HFIP, called antiperiplanar. Available spectroscopic information and ab initio calculations on five prototype molecules helped in exploring the torsional behavior of molecules having a CF3-C-CF3 group. Two-dimensional potential energy surfaces have been analyzed for all molecules, which explained the presence/absence of doubling in the rotational transitions. With the help of natural bond orbital (NBO) analysis, reasons for the conformational preference of HFIP have been explained.

Prediction of electronically nonadiabatic decomposition mechanisms of isolated gas phase nitrogen-rich energetic salt: Guanidium-triazolate

Electronically nonadiabatic decomposition pathways of guanidium triazolate are explored theoretically. Nonadiabatically coupled potential energy surfaces are explored at the complete active space self-consistent field (CASSCF) level of theory. For better estimation of energies complete active space second order perturbation theories (CASPT2 and CASMP2) are also employed. Density functional theory (DFT) with B3LYP functional and MP2 level of theory are used to explore subsequent ground state decomposition pathways. In comparison with all possible stable decomposition products (such as, N-2, NH3, HNC, HCN, NH2CN and CH3NC), only NH3 (with NH2CN) and N-2 are predicted to be energetically most accessible initial decomposition products. Furthermore, different conical intersections between the S-1 and S-0 surfaces, which are computed at the CASSCF(14,10)/6-31G(d) level of theory, are found to play an essential role in the excited state deactivation process of guanidium triazolate. This is the first report on the electronically nonadiabatic decomposition mechanisms of isolated guanidium triazolate salt. (C) 2015 Elsevier B.V. All rights reserved.

On representing chemical environments

We review some recently published methods to represent atomic neighbourhood environments, and analyse their relative merits in terms of their faithfulness and suitability for fitting potential energy surfaces. The crucial properties that such representations (sometimes called descriptors) must have are differentiability with respect to moving the atoms, and invariance to the basic symmetries of physics: rotation, reflection, translation, and permutation of atoms of the same species. We demonstrate that certain widely used descriptors that initially look quite different are specific cases of a general approach, in which a finite set of basis functions with increasing angular wave numbers are used to expand the atomic neighbourhood density function. Using the example system of small clusters, we quantitatively show that this expansion needs to be carried to higher and higher wave numbers as the number of neighbours increases in order to obtain a faithful representation, and that variants of the descriptors converge at very different rates. We also propose an altogether new approach, called Smooth Overlap of Atomic Positions (SOAP), that sidesteps these difficulties by directly defining the similarity between any two neighbourhood environments, and show that it is still closely connected to the invariant descriptors. We test the performance of the various representations by fitting models to the potential energy surface of small silicon clusters and the bulk crystal.

Orientation effects of deformed nuclei on the production of superheavy elements

Within the dinuclear system model, the effects of the relative orientations of interacting deformed nuclei on the interaction potential energy surfaces, the evaporation residue cross sections of some cold fusion reactions leading to superheavy elements are investigated. The competition between fusion and quasifission is studied to show the effect of the orientation. It turns out that the belly-belly orientation is in favor of the production of superheavy nuclei, because in the case a barrier has suppressed the quasifission and thus helped fusion.

Shell correction and pairing energies in the dinuclear system model

We investigate the dependences of the potential energy surfaces (PES) and the fusion probabilities for some cold fusion reactions leading to super-heavy elements on the nuclear shell effect and pairing energy. It is found that the shell effect plays an important role in the fusion of the super-heavy element while pairing energy's contribution is insignificant. The fusion probabilities and evaporation residue cross sections as functions of the Ge-isotope projectile bombarding Pb-208 are also investigated. It is found that evaporation residue cross sections do not always increase with the increasing neutron number of Ge-isotope

beta-delayed proton decays of Sm-133 and Yb-149

Sm-133 was produced via fusion evaporation in the reaction Ca-40+Ru-96. Its P-delayed proton decay was studied by means of "p-gamma" coincidence in combination with a He-jet tape transport system, including half-lives, proton energy spectra, gamma-transitions following the proton emissions, and the branching ratios to the low-lying states in the grand-daughter nuclei. The possible spins and parities of 133Sm were extracted by fitting the experimental data with a statistical model calculation. The configuration-constrained nuclear potential energy surfaces of Sm-133 were calculated by using the Woods-Saxon Strutinsky method. Comparing the experimental and calculated results, the spins and parities Of Sm-133 were assigned to be 5/2(+) and 1/2(-), which is reconciled with our published simple (EC+beta(+)) decay scheme Of Sm-113 in 2001. In addition, our experimental data on the beta-delayed proton decay of Yb-149 reported in Eur. Phys. J., 2001, A12: 1-4 was also analyzed by using the same method. The spin and parity of Yb-149 was assigned to be 1/2-.

beta-delayed proton decays and spin assignments for Sm-133 and Yb-149

The proton-rich isotope Sm-133 was produced via the fusion evaporation reaction Ca-40 + Ru-96. Its beta-delayed proton decay was studied by p-gamma coincidence in combination with a He-jet tape transport system, and half-lives, proton energy spectra, gamma-transitions following the proton emission, as well as beta-delayed proton branching ratios to the low-lying states in the grand-daughter nucleus were determined. Comparing the observed beta-delayed proton branching ratios with statistical model calculations, the best agreement is found assuming that only one level with the spin of 3/2 in Sm-133 decays or two levels with the spins of 1/2 and 5/2 decay with similar half-lives. The configuration-constrained nuclear potential energy surfaces of Sm-133 were calculated using the Woods-Saxon-Strutinsky method, which suggests a 1/2-ground state and a 5/2(+) isomer with an excitation energy of 120 keV. Therefore, the simple(EC+beta(+)) decay scheme of Sm-133 in Eur. Phys. J.A 11,277(2001) has been revised. In addition, our previous experimental data on the beta-delayed proton decay of Yb-149 reported in Eur. Phys. J. A 12,1 ( 2 0 0 1) was also analyzed using the same method. The spin-parity of Yb-149 is suggested to be 1/2(-).

beta-delayed proton decays of Tb-140 and Dy-140 as well as the spin and parity of Dy-143

Tb-140 and Dy-141 were produced via fusion evaporation in the reaction Ca-40+Cd-106. Their beta-delayed proton decays were studied by means of "p-gamma" coincidence in combination with a He-jet tape transport system, including half-lives, proton energy spectra, gamma-transitions following the proton emissions, and the branching ratios to the low-lying states in the grand-daughter nuclei. The ground-state spins and parities of Tb-140 and Dy-141 were extracted as 7(+/-) and 9/2(+/-), respectively, by fitting the experimental data with a statistical model calculation. The configuration-constrained nuclear potential energy surfaces (NPES) of Tb-140 and Dy-141 were calculated by using the Woods-Saxon Strutinsky method, which indicate the ground-state spins and parities of Tb-140 and Dy-147 to be 7(+) and 9/2(-), respectively. In addition, the configuration-constrained NPES of Dy-143 was also calculated by using the same method. From the NPES a 1/2(+) ground state and a 11/2(-) isomer with the excitation energy of 198keV were found. The calculated results are consistent with our experimental data on the decay of Dy-143 reported in Eur. Phys. J., 2003, A16: 347-351.

beta-delayed proton decays and spin assignments for Tb-140, Dy-141 and Dy-143

The proton-rich isotopes Tb-140 and Dy-141 were produced via the fusion evaporation reaction Ca-40+ Cd-106. Their beta-delayed proton decays were studied by p-gamma coincidence in combination with a He-jet tape transport system, and half-lives, proton energy spectra, gamma-transitions following the proton emission, as well as beta-delayed proton branching ratios to the low-lying states in the grand-daughter nuclei were determined. Comparing the experimental data with statistical model calculations, the ground-state spins of Tb-140 and Dy-141 were found to be consistent with 7 and 9/2, respectively. The configuration-constrained nuclear potential energy surfaces (NPES) of Tb-140 and Dy-141 were calculated using the Woods-Saxon-Strutinsky method, which suggest the ground-state spins and parities of Tb-140 and Dy-141 to be 7(+) and 9/2(-), respectively. In addition, the configuration-constrained NPES of Dy-143 were calculated, which predict a 1/2(+) ground state and a 11/2(-) isomer with excitation energy of 198 keV. These findings are consistent with our previous experimental data on Dy-143 reported in Eur. Phys. J. A 16, 347 (2003).

Bonding and correlation analysis of various SiCO isomers

The structural properties for various SiCO isomers in the singlet and triplet states have been investigated using CASSCF methods with a 6-311 +G* basis set and also using three DFT and MP2 with same basis set for those systems except for the linear singlet state. The detailed bonding character is discussed, and the state-state correlations and the isomerization mechanism are also determined. Results indicate that there are four different isomers for each spin state, and for all isomers, the triplet state is more stable than the corresponding singlet state. The most stable is the linear SiCO ((3)Sigma(-)) species and may be refer-red to the ground state. At the CASSCF-MP2(full)/6-311+G* level, the state-state energy separations of the other triplet states relative to the ground state are 43.2 (cyclic), 45.2 (linear SiOC), and 75.6 kcal/mol (linear CSiO), respectively, whereas the triplet-singlet state excitation energies for each configuration are 17.3 (linear SiCO), 2.2 (cyclic SiCO), 10.2 (linear SiOC), and 18.5 kcal/mol (linear CSiO), respectively. SiCo ((3)Sigma(-)) may be classified as silene (carbonylsilene), and its COdelta- moiety possesses CO- property. The dissociation energy of the ground state is 42.5 kcal/mol at the CASSCF-MP2(full)/6-311+G* level and falls within a range of 36.5-41.5 kcal/mol at DFT level, and of 23.7-28.9 kcal/mol at the wave function-correlated level, whereas the vertical IP is 188.8 kcal/mol at the CASSCF-MP2(full)/6-311+G* level and is very close to the first IP of Si atom. Three linear isomers (SiCO, SiOC, and CSiO) have similar structural bonding character. SiOC may be referred to the iso-carbonyl Si instead of the aether compound, whereas the CSiO isomer may be considered as the combination of C (the analogue of Si) with SiO (the analogue of CO). The bonding is weak for all linear species, and the corresponding potential energy surfaces are flat, and thus these linear molecules are facile. Another important isomer is of cyclic structure, it may be considered as the combination of CO with Si by the side pi bond. This structure has the smallest triplet state-singlet state excitation energy (similar to2.2 kcal/mol); the C-O bonds are longer, and the corresponding vibrational frequencies are significantly smaller than those of the other linear species. This cyclic species is not classified as an epoxy compound. State-state correlation analysis and the isomerization pathway searches have indicated that there are no direct correlations among three linear structures for each spin state, but they may interchange by experiencing two transition states and one cyclic intermediate. The easiest pathway is to break the Si-O bond to go to the linear SiCO, but its inverse process is very difficult. The most difficult process is to break the C-O bond and to go to the linear CSiO.

Theoretical studies of product polarization and state distributions of the H+HCl reaction

The angular momentum polarization and rotational state distributions of the H-2 and HCl products from the H + HCl reaction are calculated at a relative translational energy of 1.6 eV by using quasiclassical trajectories on two potential energy surfaces, one from G3 surface [T.C. Allison et al., J. Phys. Chem. 100 (1996) 13575], and the other from BW2 surface [W. Bian, H.-J. Werner, J. Chem. Phys. 112 (2000) 220]. Product rotational distributions obtained on the G3 potential energy surface (PES) are much closer to the experimental results (P.M. Aker et al., J. Chem. Phys. 90 (1989) 4795; J. Chem. Phys. 90 (1989) 4809) than the distributions calculated on the BW2 PES. The distributions of P(phi(r)) for the H-2 and HCl products obtained on the G3 PES are similar, whereas the rotational alignment effect of the H-2 product is stronger than that of the HCl product. In contrast to the polarization distributions obtained on the G3 PES, the rotational alignment effect of the two products calculated on the BW2 PES is similar. However, the abstraction reaction is dominated by out-of-plane mechanisms, while the exchange reaction is dominated by in-plane mechanisms. The significant difference of the product rotational polarization obtained on the G3 and BW2 PESs implies that the studies of the dynamical stereochemistry can provide a sensitive test for the accuracy of the PES. (C) 2002 Elsevier Science B.V. All rights reserved.

Electronic structures of MCO (M = Nb, Ta, Rh, Ir, Pd, Pt) molecules by density functional theory

Equilibrium geometries, vibrational frequencies, and dissociation energies of the transition metal carbonyls MCO (M = Nb, Ta, Rh, Ir, Pd, Pt) were studied by use of diverse density functional methods B3LYP, BLYP, B3P86, B3PW91, BHLYP, BP86, and PBE1PBE. It was found that the ground electronic state is (6)Sigma(+) for NbCO and TaCO, (2)Sigma(+) for RhCO,(2)Delta for IrCO, and (1)Sigma(+) for PdCO and PtCO, in agreement with previous theoretical studies. The calculated properties are highly dependent on the functionals employed, in particular for the dissociation energy. For most of the molecules, the predicted bond distance is in agreement with experiments and previous theoretical results. BHLYP is the worst method in reproducing the experimental results compared with the other density functional methods for the title molecules.