HIGH RESOLUTION RAMAN SPECTROSCOPY OF GASES: XI. SPECTRA OF CS2 AND CO2

1958 ◽  
Vol 36 (2) ◽  
pp. 218-230 ◽  
Author(s):  
B. P. Stoicheff
Keyword(s):  
Raman Spectroscopy ◽  
High Resolution ◽  
Raman Spectra ◽  
Rotational Structure ◽  
Rotational Spectrum ◽  
Vibrational Constants ◽  
Infrared Data

The vibrational Raman spectra of CS2, C12O2, and C13O2, consisting of the strong Fermi diad ν1, 2ν2 have been photographed with a 21 ft. grating. In the spectrum of CS2, 12 additional sharp Q branches were observed in the region of the diad; three are due to isotopic molecules and the remainder are "hot" bands. The rotational structure of the strong ν1 band was also obtained. These measurements together with infrared data are used to determine the vibrational constants ωi0 and xik of CS2. The pure rotational spectrum of CS2, with rotational lines up to J = 94, yields the constants B000 = 0.10910 ± 0.00005 cm−1, D000 = 1.0 × 10−8 cm−1, and r0(C=S) = 1.5545 ± 0.0003 Å. For C12O2, the rotational structure of the diad was analyzed and the results are in agreement with recent infrared data.

HIGH RESOLUTION RAMAN SPECTROSCOPY OF GASES: III. RAMAN SPECTRUM OF NITROGEN

1954 ◽  
Vol 32 (10) ◽  
pp. 630-634 ◽  
Author(s):  
B. P. Stoicheff
Keyword(s):  
Raman Spectroscopy ◽  
Raman Spectrum ◽  
High Resolution ◽  
Electronic Spectra ◽  
Second Order ◽  
Published Data ◽  
Rotational Spectrum ◽  
Rotational Constants ◽  
Vibrational Constants

The pure rotational spectrum and the Q branch of the 1–0 band of N2 were photographed in the second order of a 21 ft. grating. An analysis of the rotational spectrum yields the rotational constants[Formula: see text]The value of B0 together with the Bν values obtained from the electronic bands of N2 gives[Formula: see text]Revised values of the vibrational constants have also been calculated using the results of the present work and the published data on the electronic spectra.

HIGH RESOLUTION RAMAN SPECTROSCOPY OF GASES: XV. ROTATIONAL SPECTRUM AND MOLECULAR STRUCTURE OF CYCLOBUTANE

1962 ◽  
Vol 40 (6) ◽  
pp. 725-731 ◽  
Author(s):  
R. C. Lord ◽  
B. P. Stoicheff
Keyword(s):  
Molecular Structure ◽  
Raman Spectroscopy ◽  
High Resolution ◽  
Bond Length ◽  
Raman Spectra ◽  
Point Group ◽  
Rotational Spectrum ◽  
Rotational Constants ◽  
Group D

An investigation of the rotational Raman spectra of normal and fully deuterated cyclobutane (C4H8 and C4D8) has given values of the rotational constants for these molecules. From these results it was found that the C—C bond length is 1.558 ± 0.003 Å, irrespective of whether cyclobutane belongs to the molecular point group D4h (planar C4 ring) or D2d (puckered C4 ring).

HIGH RESOLUTION RAMAN SPECTROSCOPY OF GASES: I. EXPERIMENTAL METHODS

1954 ◽  
Vol 32 (5) ◽  
pp. 330-338 ◽  
Author(s):  
B. P. Stoicheff
Keyword(s):  
Raman Spectroscopy ◽  
High Resolution ◽  
Magnesium Oxide ◽  
Raman Spectra ◽  
Experimental Methods ◽  
Resolving Power ◽  
Polar Molecules ◽  
High Current ◽  
Rotational Constants ◽  
Moments Of Inertia

An apparatus for obtaining intense Raman spectra of gases excited by the Hg 4358 line is described. It consists of a mirror-type Raman tube irradiated by two high-current mercury lamps, completely enclosed in a reflector of magnesium oxide. The lamps are externally water-cooled along their entire length and emit sharp lines of high intensity.Rotational Raman spectra of gases at a pressure of 1 atm. have been photographed in the second order of a 21 ft. grating in exposure times of 6 to 24 hr. The Raman lines are sharp and a resolving power of about 100,000 has been achieved. It will be possible to resolve the rotational Raman spectra, and hence to evaluate the rotational constants of molecules having moments of inertia of up to 300 × 10−10 gm. cm.2 Such investigations will be especially useful for non-polar molecules.

HIGH RESOLUTION RAMAN SPECTROSCOPY OF GASES: VIII. ROTATIONAL SPECTRA OF ACETYLENE, DIACETYLENE, DIACETYLENE-d2, AND DIMETHYLACETYLENE

1957 ◽  
Vol 35 (4) ◽  
pp. 373-382 ◽  
Author(s):  
J. H. Callomon ◽  
B. P. Stoicheff
Keyword(s):  
Raman Spectroscopy ◽  
High Resolution ◽  
Raman Spectra ◽  
Rotational Constants ◽  
Related Molecule ◽  
Rotational Spectra ◽  
Carbon Carbon Bonds ◽  
Carbon Bonds

The pure rotational Raman spectra of acetylene (C2H2), diacetylene (C4H2 and C4D2), and dimethylacetylene (C4H6) have been photographed with a 21-ft. grating spectrograph. The rotational constants were found to be B0(C2H2) = 1.1769 cm−1, B0(C4H2) = 0.14689 cm−1, B0(C4D2) = 0.12767 cm−1, and B0(C4H6) = 0.1122 cm−1. An analysis shows that r0(C—H) in diacetylene is shorter than in acetylene and cyanoacetylene; in dimethylacetylene at least one of the carbon–carbon bonds is longer than in the closely related molecule methylacetylene.

HIGH RESOLUTION RAMAN SPECTROSCOPY OF GASES: X. ROTATIONAL SPECTRUM OF BUTATRIENE (H2C=C=C=CH2)

1957 ◽  
Vol 35 (8) ◽  
pp. 837-841 ◽  
Author(s):  
B. P. Stoicheff
Keyword(s):  
Raman Spectroscopy ◽  
Raman Spectrum ◽  
High Resolution ◽  
Rotational Constant ◽  
Rotational Spectrum ◽  
A Value

The rotational Raman spectrum of butatriene (H2C=C=C=CH2) at a pressure of 2 cm. Hg was photographed with a 21 ft. grating spectrograph. An analysis of this spectrum (based on the symmetric top approximation) yields the rotational constant [Formula: see text](B0 + C0) = 0.13141 ± 0.0001 cm−1. If the two outer C=C bonds in butatriene are assumed to have the same length as the C=C bonds in allene,namely 1.309 Å, it is found that the central C=C bond has a length of 1.284 ± 0.006 Å, a value which is shorter than that of the C=C bonds in ethylene and in allene.

HIGH RESOLUTION RAMAN SPECTROSCOPY OF GASES: VI. ROTATIONAL SPECTRUM OF SYMMETRIC BENZENE-d3

1956 ◽  
Vol 34 (4) ◽  
pp. 350-353 ◽  
Author(s):  
A. Langseth ◽  
B. P. Stoicheff
Keyword(s):  
Raman Spectroscopy ◽  
Raman Spectrum ◽  
High Resolution ◽  
Rotational Constant ◽  
Benzene Molecule ◽  
Second Order ◽  
Rotational Spectrum ◽  
Internuclear Distances

The pure rotational Raman spectrum of C6H3D3 vapor at a pressure of 15 cm. Hg was photographed in the second order of a 21 ft. grating. The value of the rotational constant was found to be B0 = 0.17165 ± 0.0001 cm−1. This result confirms the earlier spectroscopic values of the internuclear distances in the benzene molecule.

HIGH RESOLUTION RAMAN SPECTROSCOPY OF GASES: II. ROTATIONAL SPECTRA OF C6H6 AND C6D6, AND INTERNUCLEAR DISTANCES IN THE BENZENE MOLECULE

1954 ◽  
Vol 32 (5) ◽  
pp. 339-346 ◽  
Author(s):  
B. P. Stoicheff
Keyword(s):  
Raman Spectroscopy ◽  
High Resolution ◽  
Raman Spectra ◽  
Benzene Molecule ◽  
Hexagonal Structure ◽  
Second Order ◽  
Rotational Constants ◽  
Moments Of Inertia ◽  
Rotational Spectra ◽  
Internuclear Distances

The pure rotational Raman spectra of benzene and benzene–d6 at a pressure of [Formula: see text] atm. were photographed in the second order of a 21 ft. grating. Both spectra were resolved and analyzed, yielding for the rotational constants the values B0(C6H6) = 0.18960 ± 0.00005 cm.−1, B0(C6D6) = 0.15681 ± 0.00008 cm.−1and, therefore, for the moments of inertia about an axis perpendicular to the figure axis[Formula: see text]If it is assumed that the benzene molecule has the planar hexagonal structure, the moments of inertia just given yield for the internuclear distances in benzene the values[Formula: see text]

EMISSION BAND SPECTRA OF NITROGEN: A STUDY OF SOME SINGLET SYSTEMS

1957 ◽  
Vol 35 (2) ◽  
pp. 216-234 ◽  
Author(s):  
Alf Lofthus
Keyword(s):  
Electronic Structure ◽  
High Resolution ◽  
Emission Band ◽  
Rotational Structure ◽  
Electron Configuration ◽  
Excitation Energies ◽  
Local Perturbations ◽  
Singlet States ◽  
Band Spectra ◽  
Vibrational Constants

Ten bands of Gaydon's and Herman's singlet systems and eight new bands have been photographed under high resolution and analyzed in detail. Two of the new transitions were shown to be [Formula: see text], the upper state being in one case identical with Watson's and Koontz's state g, and one new transition to be 1Δg—ω1Δu in type. It is proposed that the new state 1Δg has the same electron configuration as the [Formula: see text] state. Two bands in the red and one band in the ultraviolet could not be assigned with certainty. Local perturbations in the [Formula: see text] state were observed and shown to be caused by the ν = 1 level of the [Formula: see text] state. Observed pecularities in the rotational structure of most of the upper states are proposed to be indicative of a transition from case b′ to d′ coupling. In some cases pronounced decreases in branch intensities were observed, indicating predissociations probably caused by "forbidden" intercombination processes. Identification of the electronic structure of the higher singlet states in terms of Rydberg orbitals is discussed. Rotational and vibrational constants and excitation energies are presented.

HIGH-RESOLUTION RAMAN SPECTROSCOPY OF GASES: XVIII. PURE ROTATIONAL SPECTRA OF CYCLOPROPANE AND CYCLOPROPANE-d6

1964 ◽  
Vol 42 (11) ◽  
pp. 2259-2263 ◽  
Author(s):  
W. Jeremy Jones ◽  
B. P. Stoicheff
Keyword(s):  
Raman Spectroscopy ◽  
High Resolution ◽  
Raman Spectra ◽  
Internuclear Distance ◽  
Ground State ◽  
Rotational Constants ◽  
Rotational Spectra ◽  
Resolution Study

A high-resolution study of the rotational Raman spectra of cyclopropane and cyclopropane-d6 has yielded the values 0.66962 ± 0.00020 cm−1 and 0.46079 ± 0.00015 cm−1 for their ground-state rotational constants. From these values the C–C internuclear distance is determined to be 1.514 ± 0.002 Å.

Near-Infrared Raman Spectroscopy with High Resolution Using the Scanning Multichannel Technique

1994 ◽  
Vol 48 (4) ◽  
pp. 454-457 ◽  
Author(s):  
J.-C. Panitz ◽  
F. Zimmermann ◽  
F. Fischer ◽  
W. Häfner ◽  
A. Wokaun
Keyword(s):  
Raman Spectroscopy ◽  
High Resolution ◽  
Raman Spectra ◽  
Near Infrared ◽  
Experimental Setup ◽  
Good Resolution ◽  
Multichannel Detection ◽  
Ccd Detector ◽  
Definition Of ◽  
Double Monochromator

An experimental setup has been developed for the measurement of Raman spectra with NIR excitation, which combines high resolution with multichannel detection. The instrument is based on a Ti:sapphire laser for excitation, a double monochromator, and a CCD detector. The scanning multichannel technique is used for efficient acquisition of Raman spectra. Principal features of the software designed for control of the spectrometer are described, including definition of problem-adapted resolution elements and spike-removal routines. Raman spectra of several compounds are given, demonstrating the good resolution obtainable with this version of NIR Raman spectroscopy.

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