Ab initio Hartree-Fock instabilities in closed-shell molecular systems

The Hartree-Fock instability of twelve polyatomic systems is studied at theab initio level. It is found that all the systems with at least one double bond, exhibit a non-singlet instability. On the other hand instabilities of singlet type as well as instabilities of non-real type appear only in a small number of cases. The existence of these instabilities is discussed with respect to the location of low-lying excited states and to the weight of ionic structure.     

Using of quantum-chemical calculations to molecular crystals studying

Structural Chemistry - A brief enough survey on the approaches to molecular crystal structure analysis development is presented in this review. The main focus is on the development and application...     

Simplified ab-initio calculations for molecular systems

A method is described for reducing a large part of the arithmetic of exact ab-initio SCF molecularorbital calculations based on Slater-type-orbitals without noticeable loss of numerical accuracy. The procedure involves the transformation to Löwdin orthogonalized orbitals and then invoking the NDDO approximation. The three- and four-centre two-electron integrals required are estimated by a truncated Ruedenberg expansion. All one-electron integrals are evaluated exactly. No empirical parameters are employed. Numerical tests on CO, OF₂, O₃ and ONF show that the NDDO approximation is very accurate for Löwdin functions and that the Ruedenberg expansion is arithmetically satisfactory for the SCF MO calculations.     

Shear-flow instabilities in non-flow-aligning nematic liquid crystals

This paper investigates theoretically the stability of non-flow-aligning nematics in simple shear flow by analyzing the relevant continuum equations. With the aid of numerical techniques, it proves possible to predict thresholds for instability to perturbations both within and out of the shear plane, based on the full equations without approximations. The results obtained are consistent with corresponding experimental studies.     

To the question on radiationless transitions in electronically excited zones of molecular crystals

A model is proposed describing the dynamics of radiationless transitions in the energy zones corresponding to excited electronic states in molecular crystals. In this model, the migration effect is explicitly reflected, which initially appears under pulse excitation of the systems with a periodical structure of a density distribution of states in separate parts of molecular crystals.     

Approaches to charge calculations in molecular mechanics. 2 Resonance effects in conjugated systems

A previously published scheme of estimating atomic charges in haloalkanes is extended to include olefines, alcohols amines, acids, ethers, and amides. In the conjugated systems the effects of mesomeric transfer of charge are explicitly included. Generally good agreement with the observed dipole moments of these compounds and their substituted derivatives is found. The atomic charges so obtained are compared with those of other semiempirical and quantum-mechanical calculations for the amide group. The charges so obtained fall within the range of values obtained by these other schemes, supporting the general validity of this approach.     

Accurate lattice energies of organic molecular crystals from periodic turbomole calculations

Accurate lattice energies of organic crystals are important i.e. for the pharmaceutical industry. Periodic DFT calculations with atom‐centered Gaussian basis functions with the Turbomole program are used to calculate lattice energies for several non‐covalently bound organic molecular crystals. The accuracy and convergence of results with basis set size and k‐space sampling from periodic calculations is evaluated for the two reference molecules benzoic acid and naphthalene. For the X23 benchmark set of small molecular crystals accurate lattice energies are obtained using the PBE‐D3 functional. In particular for hydrogen‐bonded systems, a sufficiently large basis set is required. The calculated lattice energy differences between enantiopure and racemic crystal forms for a prototype set of chiral molecules are in good agreement with experimental results and allow the rationalization and computer‐aided design of chiral separation processes. © 2018 Wiley Periodicals, Inc.     

Unrestricted Hartree-Fock instabilities in nuclear spin-spin coupling calculations. The MNDO method

The MNDO wavefunction is used to calculate the Fermi contact term of nuclear spin-spin coupling constants. Owing to the presence of non-singlet unrestricted Hartree-Fock instabilities of the wavefunction, convergence problems arise in a rather large set of molecules, especially those containing molecular orbitals. A special technique to cope with this situation is presented. The MNDO and transmitted components of the coupling constants in the ethylene molecule are also calculated and compared with those previously obtained with the INDO and INDO/S methods.Part of a Ph.D. thesis (G.E.S.) to be presented to the University of Buenos Aires.Commission of Scientific Research (CIC, Pcia. Bs. As.) fellow.Argentine National Research Council (CONICET) fellow.Member of the Argentine National Research Council (CONICET).     

Local density calculations of correlation energy for molecular systems

The correlation energy for various diatomic molecules is calculated employing the expressions recently proposed (R.L. Boada and V.V. Karasiov, Chem. Phys. Lett., 175 (1990) 641; R.L. Boada, J. Maldonado and V.V. Karasiov, J. Mol. Struct. (Theochem), 287 (1994) 11). The calculated correlation energies are compared with results obtained from other methods.     

Strategies for electron correlation calculations on large molecular systems

The two main problems in applying common methods for electron correlation to large systems are (1) the steep dependency of the computational task with the size of the system and (2) the large and often prohibitive number of two-electron integrals that must be stored and retrieved during the calculation. The direct local correlation method eliminates both these problems. This method is a combination of the local correlation method that eliminates the steep computational dependency with the size of the system and extension of the direct SCF approach to electron correlation methods. The latter method eliminates external storage of the electron repulsion integrals. In this review, the direct local correlation approach and its computer implementation will be described in detail, including computational examples and comparisons to similar methods developed in other groups. The feasibility of future applications to extended systems is discussed.     

Effect of triply and quadruply excited configurations on molecular one-electron densities in configuration interaction calculations

Electron correlation densities including singles, doubles, triples and quadruples in configuration interaction calculations are presented for the ground states of H₂O and N₂. The correlation densities are analysed in terms of the contributions from the various types of excitations. Comparisons with the corresponding contributions to the correlation energies are made.     

Electronic structure and excited states of molecular crystals of antimony and tellurium hexahalogenides

The article examines the electronic structure and orbital nature of luminescence excitation in a series of molecular crystals with the general formula E _n AX₆, where E _n are organic and inorganic cations (diphenylguanidinium, guanidinium, and cesium); n is the number of cations; AX₆ are Te(IV) and Sb(III) anions; X are the atoms of halogens Cl or Br. The electronic structure of these molecular crystals is determined from the data of X–ray photoelectron spectroscopy of the core and valence levels and еру quantum chemical modeling фе the density functional theory level together with the previously obtained single crystal X–ray diffraction data.     

Dynamic behavior of highly excited molecular states in the strong monochromatic laser fields

The dynamic behavior of highly excited molecular states in an external monochromatic field has been investigated in order to establish the general trends in the Rydberg state manifestations in collisional and radiative processes. The effects of interference between direct (background) and resonant interactions and coupling between the continua on the fine structure of collision cross sections and near-threshold photoabsorption spectra are discussed. Analytical expressions for the widths and intensities of the Rydberg lines induced by mixing the field with other quasistationary states are derived and their dependence on the external field strength and frequency are analyzed. It was found that the appreciable stabilization of isolated Rydberg levels observed previously in superstrong fields is also possible in fields much weaker than atomic fields. The possibility of laser control for the energy averaged cross sections and reaction rate constants are considered. All effects are illustrated for thee ^– + H₂ ⁺ system.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 367–386, March, 1994.This work was supported by the Russian Foundation for Basic ReSearch (Grant No. 93-03-4700).     

Structure and magnetic properties of nitroxide molecular crystals by density functional calculations employing periodic boundary conditions.

The structure and magnetic properties of one-dimensional chains of representative nitroxides have been studied by a density functional model employing periodic boundary conditions. The optimized geometries are in better agreement with experiments than those obtained from optimizations of model dimeric systems. The spin populations and isotropic hyperfine couplings compare well with the values measured by polarized neutron and electron spin resonance experiments. Magnetic couplings computed by the broken symmetry approach reproduce the ferro- or antiferromagnetic behavior of different nitroxides derived from experiments. These results point out the reliability of the computational model and the significant tuning of all the magnetic properties by intermolecular hydrogen bridges.     

Semi-empirical calculations of molecular trajectories: Method and applications to some simple molecular systems

The MNDO Hamiltonian as incorporated within MOPAC has been utilized to predict dynamics for some simple reactions. In one option, the intrinsic reaction coordinate has been followed along the path of steepest descent from the transition state backward to reactants and forward to products. In a second option, dynamics of isolated molecular systems have been calculated. In each case, the potential surface (as predicted by the MNDO Hamiltonian) is calculated in situ as the atomic trajectories are calculated from Newton's Laws of Motion. Several specific examples are given and discussed.