Equilibrium structure in the presence of internal rotation: A case study of cis-methyl formate

The Born-Oppenheimer (BO) equilibrium molecular structure () of cis-methyl formate has been determined at the CCSD(T) level of electronic structure theory using Gaussian basis sets of at least quadruple-ζ quality and a core correlation correction. The quadratic, cubic and semi-diagonal quartic force field in normal coordinates has also been computed at the MP2 level employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure () has been derived from experimental ground-state rotational constants and the lowest-order rovibrational interaction parameters calculated from the ab initio cubic force field. To determine structures, it is important to start from accurate ground-state rotational constants. Different spectroscopic methods, applicable in the presence of internal rotation and used in the literature to obtain “unperturbed” rotational constants from the analysis and fitting of the spectrum, are reviewed and compared. They are shown to be compatible though their precision may be different. The and structures are in good agreement showing that, in the particular case of cis-methyl formate, the methyl torsion can still be treated as a small-amplitude vibration. The best equilibrium structure obtained for cis-methyl formate is: r(C_m-O) = 1.434 Å, r(O-C_c) = 1.335 Å, r(C_m-H_s) = 1.083 Å, r(C_m-H_a) = 1.087 Å, r(C_c-H) = 1.093 Å, r(CO) = 1.201 Å, ∠(COC) = 114.4°, ∠(CCH_s) = 105.6°, ∠(CCH_a) = 110.2°, ∠(OCH) = 109.6°, ∠(OCO) = 125.5°, and τ(H_aCOC) = 60.3°. The accuracy is believed to be about 0.001 Å for the bond lengths and 0.1° for the angles.     

Group-theoretical investigation of the tunneling splitting patterns of enolic acetylacetone

Extensive experimental and theoretical studies for enolic acetylacetone have been presented in the literature, but studies of the tunneling splitting patterns are still lacking. In this work we adopt the C_s symmetry equilibrium structure and apply a group-theoretical formalism to study the tunneling splitting pattern of the ground vibrational level of enolic acetylacetone. Enolic acetylacetone has three large-amplitude motions, one intramolecular hydrogen transfer and two methyl torsions. Therefore, the C_s structure of enolic acetylacetone has 18 (3 × 3 × 2) equivalent equilibrium molecular frameworks, nine (3 × 3) of them are from the two methyl torsions, and two are from the intramolecular hydrogen transfer. Tunneling motions among the 18 equivalent molecular frameworks split the ground vibrational level into eight sublevels: A₁, A₄, E₁, E₂, E₃, E₄, G(1) and G(2). In enolic acetylacetone the intramolecular hydrogen transfer induces a rearrangement of the CC, CO single and double bonds, and then triggers two additional 60° internal rotations, one in each of the two methyl groups attached to the hydrogen-bonded malonaldehyde ring. This interaction further complicates the tunneling splitting patterns and increases the difficulty of spectral analysis. In this work the influence of the intramolecular hydrogen transfer on the energy order of the eight sublevels is determined by a group-theoretical formalism.     

Silver nanoparticles on amidoxime fibers for photo-catalytic degradation of organic dyes in waste water

Herein we report that a new photo-catalyst of silver nanoparticles attached on the surface of amidoxime fibers was developed and evaluated. The nanoparticles had different sizes from tens to hundreds of nanometers and varied shapes of cube, plate, and sphere; and there were coordination interactions between the nanoparticles and the amidoxime fibers. The developed photo-catalyst demonstrated high activities for degradation of an organic dye of methyl orange, particularly under sunlight; and the catalyst could be re-activated for several times by simple tetrahydrofuran treatment. The results also suggested that the silver nanoparticles initiated and/or mediated the photo-oxidation reaction of methyl orange through localized surface plasmon resonance under sunlight, and the photo-catalytic activities were primarily determined by sizes and/or surface-to-mass ratios instead of shapes of the silver nanoparticles.     

Morphology of IPN-like systems consisting of polyethylene and vinyl polymer

The morphology of an interpenetrating network-like (IPN-like) system consisting of polyethylene (PE) and polystyrene (PS) is compared with an IPN system consisting of PE and polymethacrylate copolymers with different lengths of alkyl groups. In the presence of dodecyl methacrylate (DMA) units in the copolymer network of the IPN-like system, increased homogeneity of the interphase was observed.     

Hydrothermal synthesis of manganese oxide and nitrogen doped graphene (NG-MnO2) nanohybrid for visible light degradation of methyl orange dye

MnO₂ nanoparticles and its nanocomposite with nitrogen-doped graphene (NG) have been fabricated via simple hydrothermal synthesis procedure using water as a solvent. X-ray diffraction (XRD) analysis of the as-prepared samples was used to ascertain the phase purity and crystallite size. Field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) were employed to study the surface features and particle size of the synthesised samples. The photocatalytic ability of the methyl orange (MO) dye with bare MnO₂ and its hybrid with nitrogen-doped graphene (NG-MnO₂) wer compared with visible light prompted degradation of the dye in absence of these catalysts. The prepared nanohybrid (NG-MnO₂) showed improved photocatalytic efficacy as compared to the pure MnO₂ nanoparticles. The strong ferromagnetic character of nanohybrid helps in easy separation of catalyst even with a bar magnet.     

Structural,electrical and optical properties of gamma irradiated methyl para-hydroxy benzoate single crystals

ABSTRACT

Nonlinear optical materials (NLO) have been garnering attention due to their role in optical data storage, optical communication and laser technology. Organic crystals have emerged as an extremely important class of NLO materials, since their NLO properties compare very well with traditional inorganic NLO materials like KCl, LiNbO₃, KDP (potassium dihydrogen phosphate), etc. They offer the additional advantage that they can be grown relatively inexpensively from solution close to room temperature, unlike the inorganic NLO materials which are grown from high temperature melts. In the present work, organic transparent single crystals of methyl para-hydroxy benzoate (MHB) were grown by slow evaporation solution growth technique (SEST) from aqueous solution at room temperature. The changes in structural, electrical and optical properties of gamma irradiated MHB single crystals were studied using X-ray diffraction (XRD), UV–Visible absorption spectroscopy, Photo-luminescence (PL), Fourier transform infrared (FTIR) spectroscopy and AC conductivity measurements at room temperature. The polished MHB single crystals were irradiated with gamma rays of doses 10 and 15 kilogray (kGy). From the XRD analysis, it was observed that gamma irradiation for these doses drastically decreases the crystallinity. The optical absorption constants were examined by UV-Visible absorption spectroscopy, measured over the wavelength range of 200–800?nm, at normal incidence. The optical band gap as estimated from the Tauc plot ((αhν)² vs hν) was found to be reduced with increasing gamma irradiation doses. PL spectra showed emission at wavelengths of 361?nm (3.43?eV) and 452?nm (2.74?eV), with enhanced intensities for the irradiated crystals. FTIR spectroscopy was utilised to identify the functional groups of MHB and indicated the rupture of specific types of bonds with gamma irradiation. Apart from that, the enhancement of AC conductivity with gamma irradiation was also observed for the gamma irradiated crystals.     

CH3NH3 + as a quantum and classical rotor

Spin-lattice relaxation time T ₁ is determined for protons in three polycrystals (CH₃NH₃)₅Bi₂Cl₁₁, (CD₃NH₃)₅Bi₂Cl₁₁ and (CH₃ND₃)₅Bi₂Cl₁₁. The temperature dependence of the relaxation times obtained for (CH₃NH₃)₅Bi₂Cl₁₁ and (CD₃NH₃)₅Bi₂Cl₁₁ are interpreted as a result of correlated motions of the three-proton groups of the monomethylammonium cation. ²H NMR lines of (CD₃NH₃)₃Sb₂Br₉ have been recorded between 5 K and 291 K using solid echo method. The ²H NMR line shape analysis shows that characteristic shape of tunnelling methyl group appears at about 25 K and coming down with temperature up to 5 K is more distinct. From theoretical calculation, it has been found that in the quadrupolar constants is 161.3 kHz and tunnelling frequency is above 3 MHz.     

Mechanistic study of the reaction of methyl peroxy radical (CH3O2) with formaldehyde (CH2O)

ABSTRACT

A direct dynamic study on the reactions of CH₃O₂?+?CH₂O was carried out over the temperature range of 300–1500?K. All stationary points were calculated with the M06-2X/6-311++G(d,p) level of theory and identified for local minimum. The energetic parameters were refined at QCISD (T)/cc-pVTZ and CCSD (T)/cc-pVTZ levels of theory. Three channels were explored and a reaction of hydrogen abstraction from CH₂O by CH₃O₂ was identified as dominant channel which involves the formation of a prereactive complex in the entrance channel. The rate coefficient of the dominant channel was calculated with TST and TST/Eck and the Eckart tunnelling effect is only important over the lower temperature region. The calculated rate coefficient of the dominant channel has positive temperature dependence and agrees reasonably with the available literature data.     

Ni/NHC-catalyzed cross-coupling of methyl sulfinates and amines for direct access to sulfinamides

It was reported to develop a simple and convenient method for the Ni/NHC-catalyzed cross-coupling of methyl sulfinates and amines without an acid/base to afford secondary or tertiary sulfinamides in moderate to good yields. The method can provide the desired products with broad substrate scope, good chemoselectivity and good functional group compatibility. The presented approach may enrich the Ni/NHC catalyst system and promote the applications of methyl sulfinates in the organic sulfur chemistry.     

Vibrational energy levels of methyl chloride calculated from full dimensional ab initio potential energy surface

The vibrational levels for two isotopic species of methyl chloride have been calculated in the region 0-3500 cm⁻¹ from the ab initio potential energy surface (PES). The isotopic shift of vibrational levels of molecules ¹²CH₃³⁵Cl and ¹²CH₃³⁷Cl has been calculated. The correlation consistent basis sets cc-pVTZ and cc-pVQZ are employed to calculate energy values for 7957 and 3758 points correspondingly from a large domain of the nine-dimensional internal coordinate space. The analytic global PES is fitted with the standard deviation of 4.5 cm⁻¹.