Search results for "Spectral"
showing 10 items of 3116 documents
ChemInform Abstract: Spectroscopic and Theoretical Studies on the Internal Rotational Barrier of 1-Acetylcyclohexene
1987
Abstract MINDO-3 molecular orbital calculations with full geometry optimization have been carried out on 1-acetylcyclohexene (ACH) in order to estimate the rotational barrier for the acetyl group, and to localize the less energetic conformation. MNDO calculations have also been carried out for comparative purposes. Both methods point to the non-delocalized structure with the two π-clouds perpendicular to the less energetic conformation. A decomposition of the barrier energy by means of Fourier analysis is made in order to characterize the contributions to the barrier. The UV spectrum of ACH has been recorded both in vapor phase and in hexane solution. These spectra are related to the one ca…
Purely Spectroscopic Determination of the Spin Hamiltonian Parameters in High-Spin Six-Coordinated Cobalt(II) Complexes with Large Zero-Field Splitti…
2019
Accurate determination of the spin Hamiltonian parameters in transition-metal complexes with large zero-field splitting (ZFS) is an actual challenge in studying magnetic and spectroscopic properties of high-spin transition metal complexes. Recent critical papers have convincingly shown that previous determinations of these parameters, based only on the magnetic data, have low accuracy and reliability. A combination of X-band electron paramagnetic resonance (EPR) spectroscopy and SQUID magnetometry seems to be a more convincing and accurate approach. However, even in this case, the accuracy of the determination of the spin Hamiltonian parameters is strongly limited. In this work, we propose …
Nonlinear optical spectra of conjugated polymers: Effect of long-range coulomb interactions
1993
Abstract Nonlinear optical spectra of conjugated polymers are theoretically studied in the Su-Schrieffer-Heeger model supplemented by long-range Coulomb interactions. Excitonic correlation for electron-hole excitations in explicitly taken into account by a standard method. Nonlinear susceptibilities χ (3) are calculated numerically with a standard sum-over-states method for finite chains (up to 1000 sites). Using moderate interaction strength, our calculations can reproduce many distinct features observed in the linear and nonlinear spectra (two-photon absorption, third-harmonic generation, and electroabsorption) of polydiacetylenes and some other polymers. Especially, a hump in the spectru…
Computer simulations of electron paramagnetic resonance spectra of P2O5Li2WO4Li2O glasses
1992
Abstract P2O5Li2WO4Li2O glasses have been synthesized and studied over a wide range of compositions. The glasses were characterized mainly by thermodifferential analysis and electron paramagnetic resonance (EPR). The EPR spectra are characterized by the presence of two signals with very different intensities, associated with the Wv (major signal) and Mov (minor signal) paramagnetic centres. The signals have been satisfactorily reproduced by computer simulation, assuming anisotropy in the g values as well as the hyperfine parameters and linewidths. EPR parameters have been extracted and indicate metallic ions located in environments close to square pyramidal.
Heat-capacity and neutron-diffraction studies of HD monolayers physisorbed on graphite
1992
Abstract The phase diagram of HD monolayers physisorbed on graphite is studied in detail by using heat-capacity and neutron-diffraction measurements. The following features are observed: At low coverages the system forms a commensurate (C) (√3 × √3)R30° phase and at coverages near monolayer completion an incommensurate (IC) two-dimensional solid phase. The order-disorder transition of the C phase belongs to the three-state Potts universality class. The C-IC transition occurs via two intermediate phases, i.e., the α phase and a novel phase, which is interpreted as an α-IC coexistence region. Though the molecule HD is a strongly incoherent neutron scatterer, for the first time elastic neutron…
First Fourier-transform ion cyclotron resonance signals of very highly charged atomic ions
1994
We report on the first application of Fourier-transform ion cyclotron resonance mass spectrometry to the very highly charged ions produced in the high-energy electron beam ion trap (SuperEBIT) at the Lawrence Livermore National Laboratory. Initial results are described, and spectra are presented from ions as highly charged as Cs53+.
Application of the open-shell size-consistent self-consistent singles and doubles configuration interaction method to multielectronic transitions in …
2000
The size-consistent self-consistent matrix dressing method has been applied on an open-shell single-configuration reference state. Once the reference state is converged, several low-lying roots can be obtained for the dressed configuration interaction (CI) matrices of appropriate symmetry. The CI matrices were built with a complete-active-space singles and doubles CI method in order to deal properly with multiconfiguration excited states. The vertical ionization and ionization–excitation transitions are obtained from the difference to the closed shell ground-state energy of the neutral molecule. The method has been applied to NH+3 and N+2 using atomic natural orbital basis sets and state-av…
Electron impact mass spectra of chlorinated methyl propanoates
1982
The mass spectral fragmentations of all eleven chlorinated methyl propanoates have been studied. Deuterium labelling and metastable ion analysis were used to elucidate the fragmentation mechanism. The molecular ion peaks of all compounds are small, except methyl 3,3-dichloropanoate (38%). In most cases α-cleavage gives the base peak [COOCH3]+, and the loss of a chlorine atom from the molecular ion is characteristic of the 3-chloro, 3,3-dichloro and 3,3,3-trichloro compounds. Metastable ions showed the losses of small neutral molecules such as CH3OH, CH2CO, CO2 and CO from the [MCl]+ ion. α-Cleavage and the loss of Cl˙ gives an intense [MCOOCH3Cl]+˙ peak, which is the base peak in the spectr…
Structures and EPR spectra of binary sulfur–nitrogen radicals from DFT calculations
2007
Abstract The scattered electron paramagnetic resonance (EPR) spectroscopic data for binary sulfur–nitrogen (S,N) radicals have been compiled and critically assessed.Many of these are inorganic rings or cages.For each species, possible equilibrium structures in the gas phase and the EPR hyperfine coupling (hfc) constants have been calculated with DFT using the B3LYP functional and basis sets of triple-ζ (or better) quality.Good agreement is obtained between calculated and measured values for the well characterized [S3N2]+ , a planar π-radical for which the s-component of the orbitals is likely to be reasonably independent of minor geometrical changes between gas-phase and condensed-phase sta…
High-resolution photoacoustic Raman spectroscopy of gases
1992
A high-resolution photoacoustic Raman spectroscopy experiment is described. The resolution achieved by using two single-mode pulsed lasers is about 0.0054 cm −1 (full width at half maximum intensity). The experiment was tested first on the v 1 /2v 2 bands of CO 2 and gave an increase of at least about one order of magnitude in the signal-to-noise ratio with respect to stimulated Raman spectroscopy at low pressure (ca. 10 Torr ≃ 1.3 kPa). The sensitivity is also demonstrated by the study of the weak hot band v 1 +v 2 −v 2 of CO 2 . In both cases, the experimental line shape is well reproduced by taking into account Doppler and collisional effects. A comparison with CARS spectra was also made