排序方式: 共有110条查询结果,搜索用时 171 毫秒
101.
An automated evolved gas detection apparatus is described consisting of a furnace, furnace temperature programmer, automatic sample changer, thermistor thermal conductivity detector, and a two channel recorder. The samples are automatically introduced into the furnace chamber, pyrolyzed to a preselected temperature limit, and then removed. After the system has cooled to a preselected lower temperature limit, the cycle is repeated. Eight samples can be studied in a sequential manner. 相似文献
102.
Quantum-state-resolved reactive-scattering dynamics of F+D(2)O-->DF+OD have been studied at E(c.m.)=5(1) kcal/mol in low-density crossed supersonic jets, exploiting pulsed discharge sources of F atom and laser-induced fluorescence to detect the nascent OD product under single-collision conditions. The product OD is formed exclusively in the v(OD)=0 state with only modest rotational excitation ( =0.50(1) kcal/mol), consistent with the relatively weak coupling of the 18.1(1) kcal/mol reaction exothermicity into "spectator" bond degrees of freedom. The majority of OD products [68(1)%] are found in the ground ((2)Pi(32) (+/-)) spin-orbit state, which adiabatically correlates with reaction over the lowest and only energetically accessible barrier (DeltaE( not equal) approximately 4 kcal/mol). However, 32(1)% of molecules are produced in the excited spin-orbit state ((2)Pi(12) (+/-)), although from a purely adiabatic perspective, this requires passage over a DeltaE( not equal) approximately 25 kcal/mol barrier energetically inaccessible at these collision energies. This provides unambiguous evidence for nonadiabatic surface hopping in F+D(2)O atom abstraction reactions, indicating that reactive-scattering dynamics even in simple atom+polyatom systems is not always isolated on the ground electronic surface. Additionally, the nascent OD rotational states are well fitted by a two-temperature Boltzmann distribution, suggesting correlated branching of the reaction products into the DF(v=2,3) vibrational manifold. 相似文献
103.
Detailed dynamical and structural information has been obtained for hydrogen-bonded (HCl)(3) clusters via high-resolution IR laser absorption spectroscopy in a supersonic slit expansion. Multiple rovibrational bands in an approximately 3000 cm(-1) HCl stretch region have been assigned and analyzed for H (35)Cl/H (37)Cl isotopomeric contributions, corresponding to excitation of (i) the degenerate antisymmetric HCl stretch in isotopically pure (H (35)Cl)(3), (ii) high- and low-frequency components of the nearly degenerate HCl stretch in H (37)Cl (H (35)Cl)(2), (iii) the low-frequency component of the corresponding HCl stretch in (H (37)Cl)(2) H (35)Cl. The isotopically pure (H (35)Cl)(3) results are in good agreement with earlier diode-laser efforts. A simple exciton model for vibrational coupling between HCl subunits is presented that indicates rapid intramolecular energy flow (beta approximately -1.89 cm(-1), tau approximately 2.8 ps) in the trimer ring, which is in good agreement with vibrationally mediated tunneling rates observed in the HCl dimer. Spectral analysis at slit jet resolution indicates a Deltanu approximately 120 MHz homogeneous line broadening and an excited-state lifetime of approximately 1.3 ns. The data is consistent with intramolecular vibrational redistribution-induced opening of the trimer followed by true predissociation to either (HCl)(2)+HCl or 3HCl on a longer time scale. 相似文献
104.
An effective protein preconcentration technique specifically designed for microliter-volume samples is presented. The preconcentration is based on the capturing of protein in its isoelectric point (pI) within an applied electric field, using a pH junction created by a discontinuous buffer system. The buffers were chosen to selectively preconcentrate proteins of neutral pI, myoglobin in this case, while removing other proteins with acidic or basic pIs. For the suppression of electro-osmotic flow (EOF) and protein adsorption, the capillary inner wall was modified with a zwitterionic phospholipid bilayer coating. A preconcentration factor of up to 1700 was obtained for a 1 microg/mL solution of myoglobin. The preconcentration was completed in approximately 20 min. Several sample introduction conditions were presented to accommodate sample volume from one to a few hundreds of microliters. The final volume of the preconcentrated sample band was estimated to be approximately 5 nL. 相似文献
105.
Hema Tresa Varghese C. Yohannan Panicker V.S. Madhavan Samuel Mathew Jarmila Vinsova Christian Van Alsenoy 《Journal of Raman spectroscopy : JRS》2009,40(9):1211-1223
FT‐IR and FT‐Raman spectra of 4‐chloro‐2‐(4‐bromophenylcarbamoyl)phenyl acetate were recorded and analyzed. The vibrational wavenumbers and corresponding vibrational assignments were examined theoretically using the Gaussian03 set of quantum chemistry codes. The red shift of the NH stretching wavenumber in the infrared (IR) spectrum from the computed wavenumber indicates the weakening of the NH bond resulting in proton transfer to the neighbouring oxygen atom. The simultaneous IR and Raman activations of the CO stretching mode give the charge transfer interaction through a π‐conjugated path. Optimized geometrical parameters of the title compound are in agreement with similar reported structures. From the optimized structure, it is clear that the hydrogen bonding decreases the double bond character of CO bond and increases the double bond character of the C N bonds. The first hyperpolarizability, predicted infrared intensities and Raman activities are reported. The calculated first hyperpolarizability is comparable with the reported values of similar derivatives and is an attractive object for future studies of non‐linear optics. The assignments of the normal modes are done by potential energy distribution (PED) calculations. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
106.
Zolot AM Harper WW Perkins BG Dagdigian PJ Nesbitt DJ 《The Journal of chemical physics》2006,125(2):21101
Exothermic reactive scattering of F atoms at the gas-liquid interface of a liquid hydrocarbon (squalane) surface has been studied under single collision conditions by shot noise limited high-resolution infrared absorption on the nascent HF(v,J) product. The nascent HF(v,J) vibrational distributions are inverted, indicating insufficient time for complete vibrational energy transfer into the surface liquid. The HF(v=2,J) rotational distributions are well fit with a two temperature Boltzmann analysis, with a near room temperature component (T(TD) approximately equal to 290 K) and a second much hotter scattering component (T(HDS) approximately equal to 1040 K). These data provide quantum state level support for microscopic branching in the atom abstraction dynamics corresponding to escape of nascent HF from the liquid surface on time scales both slow and fast with respect to rotational relaxation. 相似文献
107.
Thresiamma George Sunny Joseph Anu Tresa Sunny Suresh Mathew 《Journal of nanoparticle research》2008,10(4):567-575
Lead tungstate occurs in nature as tetragonal stolzite of scheelite (CaWO4) type and monoclinic raspite. In this work, we report, the typical growth of snowflake-like tetragonal stolzite and bamboo-leaf-like
monoclinic raspite nanocrystals of PbWO4
via a simple aqueous precipitation method and a polyol (polyethylene glycol-200) mediated precipitation method at room temperature
(27 °C). The synthesised PbWO4 nanocrystals were characterised by XRD, SEM, EDAX and TGA–DTA. The UV-Vis absorption and photoluminescence studies of PbWO4 nanocrystals in the two morphologies were performed. The nuclei of PbWO4 nanocrystals in aqueous medium self-assemble in a tetragonal manner to form the snowflake-like crystals. In polyol medium,
PbWO4 nuclei preferentially grow by oriented attachment process to form the bamboo-leaf-like morphology. The specific morphology
of the regularly assembled PbWO4 nanocrystals in the two phases finds applications in nanoelectronics and photonics. Compared to other well-known scintillators,
PbWO4 is most attractive for high-energy physics applications, because of its high density, short decay time and high irradiation
damage resistance. 相似文献
108.
109.
C. Yohannan Panicker Hema Tresa Varghese L. Ushakumary 《Journal of Raman spectroscopy : JRS》2009,40(12):2023-2030
The IR and Raman spectra of ethyl salicylate were recorded and analyzed. The surface enhanced Raman scattering (SERS) spectrum was recorded in a silver colloid. The vibrational wavenumbers of the compound have been computed using the Hartree‐Fock/6‐31G* basis. The direction of charge transfer contribution to SERS has been discussed from the frontier orbital theory. The presence of methyl modes in the SERS spectrum indicates the nearness of the methyl group to the metal surface and the presence of ring vibrations and out‐of‐plane ring modes in the SERS spectrum suggests a flat orientation of the molecule on the silver surface. The first hyperpolarizability is calculated and the calculated molecular geometry has been compared with the reported similar structures. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
110.
L. Ushakumari Hema Tresa Varghese C. Yohannan Panicker Tugba Ertan Ilkay Yildiz 《Journal of Raman spectroscopy : JRS》2008,39(12):1832-1839
Fourier transform infrared (FT‐IR) and FT‐Raman spectra of 4‐fluoro‐N‐(2‐hydroxy‐4‐nitrophenyl)benzamide were recorded and analyzed. The vibrational wavenumbers and corresponding vibrational assignments were examined theoretically using the Gaussian03 set of quantum chemistry codes. The red‐shift of the NH‐stretching wavenumber in the infrared (IR) spectrum from the computed wavenumber indicates the weakening of the NH bond resulting in proton transfer to the neighboring oxygen atom. The simultaneous IR and Raman activation of the CO‐stretching mode gives the charge transfer interaction through a π‐conjugated path. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献