Ab initio second-order algebraic diagrammatic construction (ADC(2)) calculations using the resolution of the identity (RI) method have been performed on poly-(p-phenylenevinylene) (PPV) oligomers with chain lengths up to eight phenyl rings. Vertical excitation energies for the four lowest π–π* excitations and geometry relaxation effects for the lowest excited state (S1) are reported. Extrapolation to infinite chain length shows good agreement with analogous data derived from experiment. Analysis of the bond length alternation (BLA) based on the optimized S1 geometry provides conclusive evidence for the localization of the defect in the center of the oligomer chain. Torsional potentials have been computed for the four excited states investigated and the transition densities divided into fragment contributions have been used to identify excitonic interactions. The present investigation provides benchmark results, which can be used (i) as reference for lower level methods and (ii) give the possibility to parametrize an effective Frenkel exciton Hamiltonian for quantum dynamical simulations of ultrafast exciton transfer dynamics in PPV type systems.

The present study explores the structural, charge carrier injection and transport properties of a series of thiophene-pyrrole based oligo-azomethines using density functional theory (DFT) methods. Our findings show that the presence of a bulky substituent adversely affects these properties. However, the electronic effect of substituents may be utilized to tune these properties by substitutions at suitable positions. Values of frontier orbitals, ionization energies, and electron affinities are calculated for each compound to predict the ease of charge injection from metal electrodes to these azomethines and the stabilities of their ionic forms. In addition to having large injection barriers, lack of stability of the anions may hinder the electron injection. However, most of the compounds have excellent hole injection capability. Computation of reorganization energies and electronic couplings followed by charge transfer rates and mobilities show large carrier mobilities for some of the studied compounds. Considering both the injection capability and carrier mobilities, it is found that a thiophene-pyrrole azomethine without any substituent and substituted azomethines with a methyl, methoxy or amine group at the 3 position of the pyrrole ring may act as efficient materials for the hole transport layer.

A global analytical potential energy surface for the ground state of H(3)(-) has been constructed by fitting an analytic function to the ab initio potential energy values computed using coupled cluster singles and doubles with perturbative triples [CCSD(T)] method and Dunning's augmented correlation consistent polarized valence triple zeta basis set. Using this potential energy surface, time-dependent quantum mechanical wave packet calculations were carried out to calculate the reaction probabilities (P(R)) for the exchange reaction H(-)+H(2)(v, j)-->H(2)+H(-), for different initial vibrational (v) and rotational (j) states of H(2), for total angular momentum equal to zero. With increase in v, the number of oscillations in the P(R)(E) plot increases and the oscillations become more pronounced. While P(R) increases with increase in rotational excitation from j=0 to 1, it decreases with further increase in j to 2 over a wide range of energies. In addition, rotational excitation quenches the oscillations in P(R)(E) plots.

A detailed three-dimensional time-dependent quantum dynamical study of the He+H(2) (+)(v=0-3,j=0)-->HeH(+)+H reaction is reported for different vibrational v states of H(2) (+) in its ground rotational (j=0) state over a range of translational E(trans) energies on an accurate ab initio potential energy surface published by Palmieri et al. Plots of reaction probability as a function of total energy E reveal a large number of oscillations indicating the presence of a number of reactive scattering resonances. When averaged over total angular momentum J, some of the oscillations survive, indicating that they may be amenable to experimental observation. A comparison of our present results with our earlier results on the McLaughlin-Thompson-Joseph-Sathyamurthy surface and the experimental results from different research groups reveal a good deal of agreement as well as some discrepancies between theory and experiment at the level of state-selected gas phase dynamics.

A real wave packet based time-dependent method and a statistical quantum method have been used to study the He + NeH(+) (v, j) reaction with the reactant in various ro-vibrational states, on a recently calculated ab initio ground state potential energy surface. Both the wave packet and statistical quantum calculations were carried out within the centrifugal sudden approximation as well as using the exact Hamiltonian. Quantum reaction probabilities exhibit dense oscillatory pattern for smaller total angular momentum values, which is a signature of resonances in a complex forming mechanism for the title reaction. Significant differences, found between exact and approximate quantum reaction cross sections, highlight the importance of inclusion of Coriolis coupling in the calculations. Statistical results are in fairly good agreement with the exact quantum results, for ground ro-vibrational states of the reactant. Vibrational excitation greatly enhances the reaction cross sections, whereas rotational excitation has relatively small effect on the reaction. The nature of the reaction cross section curves is dependent on the initial vibrational state of the reactant and is typical of a late barrier type potential energy profile.

Bound and quasibound states of He 2 H + and He 2 D + in three dimensions have been computed by use of a time-dependent quantum-mechanical wave packet approach for total angular momentum J ) 0. Seven bound states were found for He 2 H + and 14 for He 2 D + , as compared to five for both systems by Lee and Secrest (J. Chem. Phys. 1986, 85, 6565). The potential energy surface needed for the dynamical calculation has been computed by carrying out an ab initio calculation with coupled cluster single and double excitations with perturbative triple excitations [CCSD(T)] employing d-aug-cc-PVTZ basis set. A many-body expansion function proposed by Aguado et al. (Comput. Phys. Commun. 1998, 108, 259) was fitted to the ab initio potential energy values and the resulting fit has a root-mean-square deviation of 10.8 meV (0.25 kcal/mol).

We present the results of a full-dimensional quantum mechanical study of the rovibrational energy transfer in the collision between ortho-H2 and para-H2 in the energy range of 0.1-1.0 eV. The multiconfiguration time-dependent Hartree algorithm has been used to propagate the wave packets on the global potential energy surface by Boothroyd et al. [J. Chem. Phys. 116, 666 (2002)] and on a modification of this surface where the short range anisotropy is reduced. State-to-state attributes such as probabilities or integral cross sections are obtained using the formalism of Tannor and Weeks [J. Chem. Phys. 98, 3884 (1993)] by Fourier transforming the correlation functions. The effect of initial rotation of the diatoms on the inelastic and de-excitation processes is investigated.

Real wave packet, statistical quantum, and quasiclassical trajectory methods were employed to study the dynamics of Ne + HeH+(v 0,j 0) → He + NeH+ reaction on an ab initio potential energy surface [J. Phys. Chem. A 2013, 117, 13070–13078]. Quantum and statistical quantum calculations were performed within the centrifugal sudden (CS) approximation as well as including the Coriolis coupling (CC). Dense oscillatory structures of the quantum reaction probabilities and fair agreement between quantum and statistical cross sections suggest a complex forming mechanism for the reaction. No significant differences between cross sections obtained within the CS and CC approaches are observed. Quasiclassical trajectory results give an excellent average description of the quantum CC results. At low collision energies, there is a substantial decrease in reactivity for the reaction upon rovibrational excitation. Initial state selected rate constants for the title reaction are calculated between 20 and 1000 K, and the calculated value at 300 K agrees quite well with the available experimental result. Reaction cross sections and rate constants are also compared with those calculated via the Langevin capture model for exothermic reactions.