The vibrational Raman spectrum of compressed solid hydrogen

1979 ◽  
Vol 57 (3) ◽  
pp. 442-448 ◽  
Author(s):  
E. J. Allin ◽  
S. M. Till

The frequencies of the pure vibrational lines, Q(0) and Q(1), in the Raman spectrum of solid H2 have been measured when the solid was subjected to a number of pressures between 400 and 1000 kg cm−2, corresponding to solid densities up to ~ 1250 amagat. Most samples studied had orthohydrogen concentrations ≥ 0.60. For these the frequency of Q(0) increased as the density increased but that of Q(1) showed little change. This can be explained if it is assumed that (i) the isotropic repulsive overlap interaction between a pair of molecules increases more rapidly than the attractive dispersion-type interaction, (ii) the effect of vibrational coupling between molecules in the same J-state increases asp2, and (iii) the lowering of the excitation energy of the ν = 1,J = 1 stale by electric quadrupolar interactions increases as ρ5/3. There is evidence that at higher densities ordering of the molecular angular momenta may occur at temperatures up to 4 K. The intensity of Q(1) relative to Q(0) is further enhanced at higher densities.

1972 ◽  
Vol 50 (13) ◽  
pp. 1471-1479 ◽  
Author(s):  
William R. C. Prior ◽  
Elizabeth J. Allin

The use of an argon laser of high intensity has made it possible to observe the vibrational overtone of solid hydrogen and to study the fundamental over a wider concentration range than previously. At ortho concentrations below ~ 15% the Q1(1) line has two components. The dependence on concentration and temperature of the frequency separation and relative intensity of these components is accounted for by the quadrupolar interaction between ortho molecules. Differences in the frequency shifts of the Q1(0) and the Q1(1) and of the Q2(0) and the Q1(1) lines in mixtures of all concentrations are also related to the quadrupolar interactions. The overtone lines show almost no frequency change with concentration. This is explained by a much smaller vibrational coupling due to the isotropic interactions in the ν = 2 than in the ν = 1 state. Confirmation of this is found in the small enhancement of the intensity of Q2(1) relative to Q2(0). The measurement of the frequency of Q2(0) makes it possible to determine the parameters μ1, and μ2, specifying the change in the intramolecular potential by the isotropic interactions, from transitions involving J = 0 states alone.


1965 ◽  
Vol 26 (11) ◽  
pp. 615-620 ◽  
Author(s):  
E.J. Allin ◽  
A.H. M ◽  
V. Soots ◽  
H.L. Welsh

1993 ◽  
Vol 47 (22) ◽  
pp. 14886-14897 ◽  
Author(s):  
J. J. Miller ◽  
R. L. Brooks ◽  
J. L. Hunt

1967 ◽  
Vol 45 (11) ◽  
pp. 3589-3595 ◽  
Author(s):  
A. H. Mckague Rosevear ◽  
G. Whiting ◽  
Elizabeth J. Allin

In the absence of molecular interaction the ratio of the intensity of the Q1(1) to that of the Q1(0) vibrational line in the Raman spectrum of solid hydrogen should be equal to the ratio of the number of ortho to the number of para molecules. The measured ratio at 2 °K has been found to be two to three times greater than this (Soots et al. 1965). The same anomaly is shown to be present at ~13.5 °K and also in the spectrum of the liquid. In the spectrum of solid deuterium the anomaly is much greater; the intensity ratio varies from 9.3 times the number ratio for n-D2 to 50 times the number ratio for 3.7% para-D2. The S1(0) and S1(1) lines do not show any corresponding anomaly. The experimental observations can be explained by the theory of vibrational interaction between ortho and para molecules developed recently by James and Van Kranendonk (1967a, b).


1965 ◽  
Vol 43 (10) ◽  
pp. 1836-1842 ◽  
Author(s):  
A. D. May ◽  
J. D. Poll

The influence of the lattice vibrations on the shift of the vibrational Raman lines in solid hydrogen and the influence of nonadditive intermolecular forces on the shift in hydrogen gas are investigated for freely rotating molecules in terms of the adiabatic approximation. It is shown that the experimental value for the shift in the solid (Soots et al. 1965) can be accounted for by introducing a reasonable value for the amplitude of the lattice vibrations. The effect of the nonadditive intermolecular forces on the shift in hydrogen gas is shown to be appreciable at high densities.


1978 ◽  
Vol 56 (2) ◽  
pp. 240-245 ◽  
Author(s):  
D. J. Phelps ◽  
R. G. Carriere ◽  
K. Kumar ◽  
P. R. Carey

Resonance and preresonance Raman spectra of nine substituted trans-4-benzylidene- Δ2-oxazolin-5-ones are reported. The seven analogs with phenyl in the 2 position of the oxazolinone ring have either an electron donating or attracting group on one of the phenyl rings. Although shifts in λmax of up to 100 nm are observed the Raman spectra are very similar to that of the unsubstituted trans isomer. However, in the substituted compounds modes from the benzylidene portion may become weakly intensity enhanced. Replacing the 2-phenyl group by 2-methyl in the oxazolinone ring results in quite gross changes in the Raman spectrum. Substitution by 15N in the ring of a 2-methyloxazolinone reveals that a change in the vibrational coupling scheme occurs. Excitation profiles for the 2-phenyl and the 2-methyl analogs of 4-(p-nitrobenzylidene)oxazolinone indicate that in each compound ail intensity enhanced modes are coupled to the intense low energy absorption band near 350 nm and the intensity enhancement fits the FB2 terms of Albrecht and Hutley. However, differences in the relative intensity of the benzylidene nitro feature in the 2-methyl and 2-phenyl analogs, taken with the excitation profiles, suggest that in the 2-methyl compound the electronic transition responsible for Raman intensity enhancement is no longer primarily located in the C=C—N=C—Ph moiety.


2015 ◽  
Vol 5 (1) ◽  
Author(s):  
Dahyun Nam ◽  
Jae-Ung Lee ◽  
Hyeonsik Cheong

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