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: 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: IV. ROTATIONAL RAMAN SPECTRUM OF CYANOGEN

1954 ◽  
Vol 32 (10) ◽  
pp. 635-638 ◽  
Author(s):  
C. K. Møller ◽  
B. P. Stoicheff
Keyword(s):  
Raman Spectroscopy ◽  
Raman Spectrum ◽  
High Resolution ◽  
Bond Length ◽  
Second Order ◽  
Single Bond ◽  
Rotational Constants ◽  
A Value ◽  
Symmetric Molecule ◽  
Concave Grating

The rotational Raman spectrum of cyanogen gas at [Formula: see text] atm. pressure has been photographed in the second order of a 21 ft. concave grating spectrograph. The simplicity of the spectrum and the observed intensity alternation of the lines show that C2N2 is a linear symmetric molecule. An analysis of the spectrum yields for the rotational constants[Formula: see text]By assuming a value for the C≡N bond length of 1.157 Å, the length of the C—C single bond was calculated to be 1.380 Å.

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: 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: 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]

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: V. ROTATIONAL SPECTRA OF ALLENE, ALLENE-d4, AND ALLENE-1,1-d2

1955 ◽  
Vol 33 (12) ◽  
pp. 811-818 ◽  
Author(s):  
B. P. Stoicheff
Keyword(s):  
Raman Spectroscopy ◽  
Double Bond ◽  
High Resolution ◽  
Raman Spectra ◽  
Second Order ◽  
Rotational Constants ◽  
Rotational Spectra ◽  
A Value ◽  
Carbon Double Bond

The pure rotational Raman spectra of allene, allene-d4 and allene-1,1-d2 were photographed in the second order of a 21 ft. grating. Two plates of each spectrum were analyzed yielding the following values for the rotational constants:[Formula: see text]These constants lead to the value r0(C=C) = 1.3088 ± 0.001 Å. Also if a value of r0(C—H) = 1.07 ± 0.01 Å is assumed, then [Formula: see text]. It is noted that the length of the carbon–carbon double bond in allene is significantly shorter than that in ethylene.

HIGH RESOLUTION RAMAN SPECTROSCOPY OF GASES: VII. ROTATIONAL SPECTRA OF s-TRIAZINE AND s-TRIAZINE-d3

1956 ◽  
Vol 34 (10) ◽  
pp. 1016-1021 ◽  
Author(s):  
J. E. Lancaster ◽  
B. P. Stoicheff
Keyword(s):  
Raman Spectroscopy ◽  
High Resolution ◽  
Bond Length ◽  
Raman Spectra ◽  
Structural Parameters ◽  
Second Order ◽  
Rotational Constants ◽  
Rotational Spectra

The pure rotational Raman spectra of s-triazine (C3H3N3) and s-triazine-d3 (C3D3N3) vapor were photographed in the second order of a 21-ft. grating spectrograph. The rotational constants were found to be B0(C3D3N3) = 0.21460 ± 0.00008 cm−1 and B0(C3D3N3) = 0.19358 ± 0.00015 cm−1. These values, together with the assumption that the molecule is planar and has a CH bond length of 1.084 Å, give the following values for the structural parameters: r0(CN) = 1.338 ± 0.001 Å, [Formula: see text]NCN = 127°, and [Formula: see text]CNC = 113°.

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: XIII. ROTATIONAL SPECTRA AND STRUCTURES OF THE ZINC-, CADMIUM-, AND MERCURY-DIMETHYL MOLECULES

1960 ◽  
Vol 38 (11) ◽  
pp. 1516-1525 ◽  
Author(s):  
K. Suryanarayana Rao ◽  
B. P. Stoicheff ◽  
R. Turner
Keyword(s):  
Raman Spectroscopy ◽  
High Resolution ◽  
Rotational Constants ◽  
Carbon Bond ◽  
Rotational Spectra ◽  
Bond Lengths ◽  
Zinc Cadmium ◽  
Symmetric Top Molecules

The pure rotational spectra of gaseous Zn(CH3)2, Cd(CH3)2, Hg(CH3)2, and of the fully deuterated molecules have been photographed with a 21-ft grating. The spectra are typical of symmetric top molecules and consist of many evenly spaced rotational lines having a separation of about 0.45 cm−1. An analysis of the spectra yielded the rotational constants (in cm−1)[Formula: see text]From these constants the following metal—carbon bond lengths were determined: Zn—C = 1.929 Å, Cd—C = 2.112 Å, and Hg—C = 2.094 Å. Relations for the C—H bond lengths and HCH angles were also obtained.

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