Search results for "Intermolecular"
showing 10 items of 396 documents
How Well Can Coarse-Grained Models of Real Polymers Describe Their Structure? The Case of Polybutadiene
2015
Coarse-graining of chemical structure of macromolecules in the melt is investigated using extensive molecular dynamics simulation data which are based on a united atom force-field model of polybutadiene. Systematically increasing the number, n, of the united atoms approximated by an effective coarse-grained monomer, we study the influence of degree of coarse-graining on the structure functions such as the segment-segment intermolecular and intramolecular correlation functions. These results are compared to Monte Carlo simulations of the corresponding coarse-grained bead-spring model and Chen-Kreglewski potential for chain molecules. In contrast to the atomistic chemically realistic model of…
Intermolecular coupling influence on conformations of molecules in solution
1994
Abstract The influence of non-specific intermolecular interactions on conformational equilibria of organic molecules is investigated with the help of the London-Debye-Keesom pair coupling potentials. It is shown that in a series of apolar solvents equilibrium constant logarithms are proportional to ζα ≡ Z αs/ R 6s,d, and in a series of polar solvents equilibrium constants logarithms are proportional to ζμ ≡ Z μ2s/ R 6s,d, where Z is the average number of neighbours of a solute molecule in the first coordination sphere, αs is the polarizability, μs the dipole moment of solvent molecules, and R s,d = R s + R d is the sum of the radii of spherical volumes per molecule of solvent (s) and dissol…
Structure and Matrix Isolation Infrared Spectrum of Formyl Fluoride Dimer: Blue-Shift of the C−H Stretching Frequency
2006
Infrared spectroscopy (IR) of formyl fluoride (HCOF) dimer is studied in low-temperature argon and krypton matrixes. New IR absorptions, ca. 17 cm(-1) blue shifted from the monomer C-H stretching fundamental, are assigned to the HCOF dimer. The MP2/6-311++G calculations were utilized to define structures and harmonic frequencies of various HCOF dimers. Among the four optimized structures, the dimer having two C-H...O hydrogen bonds possesses strongest intermolecular bonding. The calculated harmonic frequencies of this dimer structure are shifted from the monomer similarly as observed in the experiment. Thus, we suggest that the experimentally observed blue shifted C-H bands belong to the di…
Intermolecular structure factors of macromolecules in solution: Integral equation results
1999
The inter-molecular structure of semidilute polymer solutions is studied theoretically. The low density limit of a generalized Ornstein-Zernicke integral equation approach to polymeric liquids is considered. Scaling laws for the dilute-to-semidilute crossover of random phase (RPA) like structure are derived for the inter-molecular structure factor on large distances when inter-molecular excluded volume is incorporated at the microscopic level. This leads to a non-linear equation for the excluded volume interaction parameter. For macromolecular size-mass scaling exponents, $\nu$, above a spatial-dimension dependent value, $\nu_c=2/d$, mean field like density scaling is recovered, but for $\n…
Tautomerism of Diazepines Fused with Pyrimidine Rings.
2003
The tautomerism of 1,4-diazepines fused with pyrimidine rings was studied by means of nmr spec-troscopy, X-ray analysis and quantum chemical calculations. It was found that in the case of 6,8-diphenyl-pyrimido[4,5-b][1,4]diazepin-4-ols (7a - e) the enamine form is more stable than the diimine form. This result is rationalized with the electron-withdrawing effect of the 4-hydroxypyrimidine ring and with the formation of intermolecular hydrogen bonds. In contrast to 7a - e, the 6,8-diaryl-2,3,4,7-tetrahydro-1,3-dimethyl-1H-pyrimido[4,5-b][1,4]diazepine-2,4-diones (9a, c, f) exist in the diimine form.
Tuning the Kondo resonance in two-dimensional lattices of cerium molecular complexes
2018
International audience; Cerium intermetallics have raised a lot of interest for the past forty years thanks to their very unusual and interesting electronic and magnetic properties. This can be explained by the peculiar electronic configuration of Ce (4f1) that allows different oxidation states leading to singular behavior such as quantum phase transitions, heavy-fermion behavior and the Kondo effect. In this work, we used a mixed-valence molecular analogue to study the Kondo effect down to the atomic scale by means of scanning tunneling microscopy/spectroscopy (STM/STS) for which new many-body effects are expected to emerge due to reduced dimensionality and specific chemical environment of…
Oligophenylenevinylenes in Spatially Confined Nanochannels: Monitoring Intermolecular Interactions by UV/Vis and Raman Spectroscopy
2008
Perhydrotriphenylene-based channel-forming inclusion compounds (ICs) and thin films made of polyphenylenevinylene (PPV)-type oligomers with terminal alkoxy groups are investigated and compared in a combined experimental and theoretical approach. Interchromophore interactions and host-guest interactions are elucidated by UV/Vis and Raman spectroscopy. The impact of the local environment of the chromophore on the optical and photophysical properties is discussed in light of quantum-chemical calculations. In stark contrast to thin films where preferential side-by-side orientation leads to quenching of photoluminescence (PL) via non-emissive traps, the ICs are found to be attractive materials f…
Intermolecular potential and rovibrational states of the H2O–D2 complex
2012
International audience; A five-dimensional intermolecular potential for H2O-D-2 was obtained from the full nine-dimensional ab initio potential surface of Valiron et al. [P. Valiron, M. Wernli, A. Faure, L. Wiesenfeld, C. Rist, S. Kedzuch, J. Noga, J. Chem. Phys. 129 (2008) 134306] by averaging over the ground state vibrational wave functions of H2O and D-2. On this five-dimensional potential with a well depth D-e of 232.12 cm (1) we calculated the bound rovibrational levels of H2O-D-2 for total angular momentum J = 0-3. The method used to compute the rovibrational levels is similar to a scattering approach-it involves a basis of coupled free rotor wave functions for the hindered internal r…
Quantitative characterization of group electrophilicity and nucleophilicity for intramolecular Diels–Alder reactions
2010
In a previous work (L. R. Domingo, M. J. Aurell, P. Perez and R. Contreras, Tetrahedron 2002, 58, 4417) we proposed that the difference in global electrophilicity index be taken as a measure of the polarity at the transition state in intermolecular Diels-Alder reactions. We herein extend this model to deal with intramolecular Diels-Alder (IMDA) processes. The transferability of the empirical reactivity rules established for the intermolecular DA reactions to the IMDA reactions is discussed. The analysis based on group electrophilicity and nucleophilicity in general fails because having two different reactivity patterns within the same molecule hampers a clean classification of electrophilic…
Complexes of HXeY with HX (Y, X = F, Cl, Br, I) : Symmetry-Adapted Perturbation Theory Study and Anharmonic Vibrational Analysis
2023
A comprehensive analysis of the intermolecular interaction energy and anharmonic vibrations of 41 structures of the HXeY· · · HX (X, Y = F, Cl, Br, I) family of noble-gas-compound complexes for all possible combinations of Y and X was conducted. New structures were identified, and their interaction energies were studied by means of symmetry-adapted perturbation theory, up to secondorder corrections: this provided insight into the physical nature of the interaction in the complexes. The energy components were discussed, in connection to anharmonic frequency analysis. The results show that the induction and dispersion corrections were the main driving forces of the interaction, and that their…