Analysis of tunable diode-laser spectra of Q(J,0) lines in CH3F near 1475 cm using a multispectrum fitting technique

We have analyzed the methyl fluoride ^RQ(J,0)Q branch lines located near 1475 cm⁻¹ using a simultaneous multi-spectrum fitting technique. In this analysis we have used previously recorded diode-laser data in which we collected many data points covering only one or two Q branch lines in a particular run. The analysis consists of simultaneously fitting 57 spectra collected with numerous pressure and path length conditions for all absorption lines. The data are concatenated to create one continuous spectrum of the Q branch. We have determined the intensity and self-broadened widths at 296 K for 23 ^RQ(J,0) lines.     

Studies on the blends of cardanol-based epoxidized novolac resin and CTPB

Cardanol-based novolac-type phenolic resins were synthesized with different mole ratios of cardanol-to-formaldehyde, viz., 1:0.6, 1:0.7, and 1:0.8. These novolac resins were epoxidized with molar excess of epichlorohydrin at 120 °C in basic medium. The epoxidized novolac resins were, separately, blended with different weight ratios of carboxyl-terminated polybutadiene liquid rubber ranging between 0-25 wt% with an interval of 5 wt%. All the blends were cured at 150 °C with 40 wt% polyamide. The formation of various products during the curing of blend samples has been studied by Fourier-transform infra-red spectroscopic analysis. The tensile strength and elongation-at-break of the cured samples increased up to 15 wt% in the blend and decreased thereafter. This blend sample was also found to be most thermally stable system. The blend morphology, studied by scanning electron microscopy analysis, was finally correlated with the structural and property changes in the blends.     

Spectral shift function and trace formula

The complete proofs of Krein’s theorem on the spectral shift function and the trace formula are given for a pair of self-adjoint operators such that either (i) their difference is trace-class or (ii) the difference of their resolvents is trace-class. The proofs, essentially due to Krein, is based on Herglotz’s theorem on the boundary value of the analytic functions whose imaginary part is non-negative on the upper half plane, and an almost optimal class of functions are obtained for which the trace formula is valid. Also an alternative method based on Weyl-von Neumann’s theorem for self-adjoint operators, avoiding the complex function theory and inspired by Voiculescu’s work, is given for the first case. Furthermore, some applications of the spectral shift function have been discussed.     

Protonation constant of salicylidene (N-benzoyl)glycyl hydrazone and its coordination behaviour towards some bivalent metal ions

Protonation constant of an unsymmetrical Schiff base, salicylidene(N-benzoyl)glycyl hydrazone (SalBzGH), and formation constants of its complexes have been determined potentiometrically at different temperatures in aqueous dioxane medium. Complexes of SalBzGH with VO(IV), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) have been prepared. Elemental analyses, pH-metric, molar conductance, magnetic susceptibility, electronic, IR, ESR, XRD (powder) and NMR studies have been carried out to study the coordination behaviour of SalBzGH toward these metal ions. pH-metric and 1H NMR studies show the presence of two dissociable protons in the ligand. IR and NMR spectra suggest the tridentate nature of the ligand, coordinating as a uninegative species in the Mn(II) complex and as a dinegative species in all the other complexes. Presence of two different conformers of the ligand at room temperature and stabilization of a single conformer upon complex formation have been established from¹H NMR spectra of the metal-free ligand, Zn(II) and Hg(II) complexes recorded at 296 K. Electronic and ESR spectra indicate highly distorted tetragonal geometry for VO(IV) and Cu(II) complexes. XRD powder patterns of the Zn(II) complexes are indexed for an orthorhombic crystal system.     

Kinetics and mechanism of the oxidation of acetaldehyde by chromic acid in perchloric acid

Summary The oxidation of MeCHO by chromium(VI) has been studied in HClO₄ medium over a wide range of experimental conditions and has been found to obey the rate law;v=k[MeCHO][HCrO ₄ ^– ][H⁺]. The calculated H and-S values for the reaction are 30±2kJ mol^–1 and 171±7J mol^–1deg^–1, respectively. The mechanism is discussed in terms of carbon-hydrogen bond cleavage.     

Use of a chiral surfactant for enantioselective reduction of a ketone

The influence of a chiral surfactant and a polymer-supported chiral additive on reduction of ketones using sodium borohydride will be described. Initial preparations involved methylation of (S)-leucinol to give (2S)-N , N-dimethyl-2-amino-4-methyl-1-pentanol (1) (67%). The chiral surfactant (2) was synthesized by reacting (1) with bromohexadecane (71%). The functionalized styrene for the polymer-supported chiral additive (5) was synthesized by reacting (1) with 4-vinylbenzyl chloride. Polymerization was carried out with 10% of the functionalized monomer (4), 5% cross-linking agent divinylbenzene, and 85% styrene with AIBN as the initiator. The activity of the chiral surfactant and polymeric additive were examined by using them as additives in a standard reduction of 2-pentanone with sodium borohydride to yield (R)- and (S)-2-pentanol (3) (20%). The resulting alcohol was analyzed by polarimetry (ee 9.5%) and also esterified with (2S)-methylbutyric acid prior to characterization by NMR. 13C NMR indicated an enantiomeric excess of 5.2% when the chiral surfactant was used, and 7% when the polymeric additive was used.     

Structural features of some small carbonyls in the 1,3nπ states: An mcscf study

Structural features of a series of tetraatomic carbonyls in the ^1,3nπ* states are studied by using a recently proposed MCSCF algorithm at the INDO/2 level. The computed geometrical parameters and the inversion barrier heights agree quite well with the available experimental or ab initio theoretical data. The calculated transition energies turn out to be somewhat lower than the experimental counterparts. The specific MCSCF algorithm used is found to have excellent convergence properties.     

Stop times in fock space stochastic calculus

Summary A stop time S in the boson Fock space over L ₂()₊ is a spectral measure in [0,] such that {S([0,t])} is an adapted process. Following the ideas of Hudson [6], to each stop time S a canonical shift operator U ^Sis constructed in . When S({}) has the vacuum as a null vector U ^Sbecomes an isometry. When S({})=0 it is shown that admits a factorisation _S]{S where _{S is the range of U ^Sand _S] is a suitable subspace of called the Fock space upto time S. This, in particular, implies the strong Markov property of quantum Brownian motion in the boson as well as fermion sense and the Dynkin-Hunt property that the classical Brownian motion begins afresh at each stop time. The stopped Weyl and fermion processes are defined and their properties studied. A composition operation is introduced in the space of stop time to make it a semigroup. Stop time integrals are introduced and their properties constitute the basic tools for the subject.     

Spectroscopic and structural features of small thiocarbonyl molecules in low-lying excited states: Further applications of a variant of the orthogonal gradient method

Structural parameters of a set of five thiocarbonyl molecules in the lowest nπ* states are calculated by using a generalized orbital optimization algorithm (a variant of the orthogonal gradient method) in an INDO MCSCF framework. Transition energies, singlet-triplet splittings, planar inversion barriers, and dipole moments in nπ* states of different spin multiplicities are reported. Predicted structural features agree reasonably well with available experimental or theoretical data. Some interesting trends are noted in the computed inversion barrier heights, singlet-triplet splittings, and dipole moments in nπ* states.