Optical absorption spectra of linear and cyclic thiophenes—selection rules manifestation

We theoretically study the size-dependent relation between absorption spectra of thiophene-based oligomers and the corresponding cyclothiophenes. In our approach based on a Frenkel exciton Hamiltonian, we demonstrate that the geometry and selection rules determine the observed relations between the spectra.     

New theoretical insight into the interactions and properties of formic acid: development of a quantum-based pair potential for formic acid

We performed ab initio quantum-chemical studies for the development of intra- and intermolecular interaction potentials for formic acid for use in molecular-dynamics simulations of formic acid molecular crystal. The formic acid structures considered in the ab initio studies include both the cis and trans monomers which are the conformers that have been postulated as part of chains constituting liquid and crystal phases under extreme conditions. Although the cis to trans transformation is not energetically favored, the trans isomer was found as a component of stable gas-phase species. Our decomposition scheme for the interaction energy indicates that the hydrogen-bonded complexes are dominated by the Hartree-Fock forces while parallel clusters are stabilized by the electron correlation energy. The calculated three-body and higher interactions are found to be negligible, thus rationalizing the development of an atom-atom pair potential for formic acid based on high-level ab initio calculations of small formic acid clusters. Here we present an atom-atom pair potential that includes both intra- and inter molecular degrees of freedom for formic acid. The newly developed pair potential is used to examine formic acid in the condensed phase via molecular-dynamics simulations. The isothermal compression under hydrostatic pressure obtained from molecular-dynamics simulations is in good agreement with experiment. Further, the calculated equilibrium melting temperature is found to be in good agreement with experiment.     

The effect of electron detachment on the structure and properties of the chlorine-acetonitrile anionic complex

The results of the theoretical study of ground state potential energy surfaces for the chlorine-acetonitrile anion and its photodetachment product are presented. The shallow potential surfaces allow for the nondefinitive position of the chlorine within the complex. The dissociation energy of the neutral complex, estimated through the thermodynamic cycle, indicates significant structural changes due to the photodetachment process. The excess negative charge is localized mostly on the chlorine atom, and the electron detachment proceeds as an electron is removed from chlorine. The process leads to drastic changes in the electrostatic interactions within the complex. The first electronic excited state corresponds to the excess electron transfer from chlorine to acetonitrile fragment. This state is a precursor of the observed charge-transfer-to-solvent state.     

Low-temperature dynamics of weakly localized Frenkel excitons in disordered linear chains

We calculate the temperature dependence of the fluorescence Stokes shift and the fluorescence decay time in linear Frenkel exciton systems resulting from the thermal redistribution of exciton population over the band states. The following factors, relevant to common experimental conditions, are accounted for in our kinetic model: (weak) localization of the exciton states by static disorder, coupling of the localized excitons to vibrations in the host medium, a possible nonequilibrium of the subsystem of localized Frenkel excitons on the time scale of the emission process, and different excitation conditions (resonant or nonresonant). A Pauli master equation, with microscopically calculated transition rates, is used to describe the redistribution of the exciton population over the manifold of localized exciton states. We find a counterintuitive nonmonotonic temperature dependence of the Stokes shift. In addition, we show that depending on experimental conditions, the observed fluorescence decay time may be determined by vibration-induced intraband relaxation, rather than radiative relaxation to the ground state. The model considered has relevance to a wide variety of materials, such as linear molecular aggregates, conjugated polymers, and polysilanes.     

Formulation of the LCAS MS SCF method within the Gaussian basis set

Within the presented LCAS MS (linear combination of atomic spinors–molecular spinors) SCF formalism both large and small components of the spinor radial parts have been expanded within the Gaussian basis set. The respective expressions for matrix elements as well as for one- and two-electron integrals are given.     

Ab initio MRD-CI calculations for breaking a chemical bond in a molecule in a crystal or other solid environment. III. Me2N?NO2 decomposition of dimethylnitramine in a large crystalline environment

Recently we extended our strategy for MRD-CI (multireference double excitation-configuration interaction) calculations, based on localized/local orbitals and an “effective” CI Hamiltonian, for molecular decompositions of large molecules to breaking a chemical bond in a molecule in a crystalline or other solid environment. Our technique begins with an explicit quantum chemical SCF calculation for a reference molecule surrounded by a number of other molecules in the multipole environment of more distant neighbors. The resulting canonical molecular orbitals are then localized, and the localized occupied and virtual orbitals in the region of interest are included explicitly in the MRD-CI with the remainder of the occupied localized orbitals being folded into an “effective” CI Hamiltonian. The MRD-CI calculations are then carried out for breaking a bond in the reference molecule. This method is completely general in that the space treated explicitly, as well as the surrounding space, may contain voids, defects, deformations, dislocations, impurities, dopants, edges and surfaces, boundaries, etc. Dimethylnitramine is the smallest prototype of the energetic R₂N—NO₂ nitramines, such as the 6-member ring RDX or the 8-member ring HMX. Decomposition of energetic compounds is initiated in the solid by a breaking of the target bond. Thus, it is crucial to know the difference in energy between breaking a bond in an isolated energetic molecule versus in the molecule in a solid. In the present study, we have carried out MRD-CI calculations for the Me₂N—NO₂ dissociation of dimethylnitramine in a dimethylnitramine crystal. The cases we investigated were one dimethylnitramine molecule (surrounded by 53 and 685 neighboring dimethylnitramine molecules represented by multipoles), three dimethylnitramine molecules, and three dimethylnitramine molecules (surrounded by 683 neighbors). All multipoles were cumulative atomic multipoles up through quadrupoles. The MRD-CI calculations on dimethylnitramine required large numbers of reference configurations from which were allowed all single and double excitations.     

Addition of benzylic and allylic organozinc and Grignard reagents to resin-bound imines to provide alpha-branched secondary amines bearing a wide variety of functional groups. Utility in the synthesis of beta-3 adrenergic receptor agonists

Benzylic and allylic organozinc and Grignard reagents have been added to resin-bound imines to provide alpha-branched secondary amines. Many functional groups, including electrophilic groups, were compatible with this methodology. Three modules--a resin-bound primary amine, an aromatic aldehyde, and the organometallic--were independently varied to produce a combinatorial library of alpha-branched secondary amines designed as beta-3 adrenergic receptor agonists.     

A new strategy for the construction of the imidazo[1,5-a]quinoxalin-4-one ring system and its application to the efficient synthesis of BMS-238497, a novel and potent Lck inhibitor

A new efficient strategy was developed for the construction of the imidazo[1,5-a]quinoxalin-4-one ring system. The new method involves condensation of o-nitroaniline with glyoxylate in methanol followed by treatment of the resulting alpha-(o-nitroanilino)-alpha-methoxy acetate with tosylmethyl isocyanide (TosMIC) reagent to give 1-(o-nitrophenyl)imidazole-5-carboxylate. Reductive cyclization of the nitro imidazole carboxylate afforded imidazo[1,5-a]quinoxalin-4-one in three steps and 60% overall yield. The new method was successfully applied to the synthesis of BMS-238497, a novel and potent Lck inhibitor.     

Oxidation properties of β-substituted pyrroles

Pyrroles represent building blocks of conjugated poly(heterocycles) which, as organic conductors, are potential materials for organic electronics. Oxidation of β-substituted pyrroles constitutes an important first step in the process of electropolymerization. Ionization energy and the electron spin density distribution are two the most important properties regarding monomers. These properties are studied as a function of electron-withdrawing and electron-donating substituents of pyrrole ring. Evolution of molecular structure, nature of bonding, and electronic density are studied as an effect of ionization process.     

Temperature dependent fluorescence in disordered Frenkel chains: interplay of equilibration and local band-edge level structure

We model the optical dynamics in linear Frenkel exciton systems governed by scattering on static disorder and lattice vibrations and calculate the temperature dependent fluorescence spectrum and lifetime. The fluorescence Stokes shift shows a nonmonotonic behavior with temperature, which derives from the interplay of the local band-edge level structure and thermal equilibration. The model yields excellent fits to experiments performed on linear dye aggregates.