Abstract

The spectrometer and experimental methods described in a companion paper were used to measure the center frequencies of some absorption lines in the HF fundamental and first-overtone bands and to measure the pressure-broadened shapes of some lines in the fundamental. The centers of both bands were calculated, and strongly J-dependent, pressure-induced line center shifts were measured for the fundamental. A method for correcting the measured shape of a spectral line for the effects of instrumental broadening in order to obtain the “true shape” is explained. It was possible to obtain the true shape of lines whose pressure broadened half-width was as small (0.03 cm−1) as several times the Doppler half-width.

It was found that the true line shape could be represented quite satisfactorily by a modified form of the Lorentz expression, i.e., α=α0ν)2[|νν0|η+(Δν)2]−1. For spectral lines whose half-width at one-half the maximum percent absorptance was less than 2.25 cm−1, η=2 gave good agreement between the true shape and that predicted by the Lorentz expression. If this width was greater than 3 cm−1 then η=1.85 allowed the best fit to the true line shape. No pressure dependence of η could be measured in the range of pressures used (0–5 atm).

© 1962 Optical Society of America

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References

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  1. J. A. Herndon, W. E. Deeds, N. M. Gailar, W. F. Herget, R. J. Lovell, and A. H. Nielsen, J. Opt. Soc. Am. 52, 1108 (1962).
    [Crossref]
  2. D. F. Smith, J. Mol. Spectroscopy 3, 473 (1959).
    [Crossref]
  3. W. S. Benedict, R. Herman, G. E. Moore, and S. Silverman, Can. J. Phys. 34, 850 (1956).
    [Crossref]
  4. G. A. Kuipers, J. Mol. Spectroscopy 2, 775 (1958).
    [Crossref]
  5. D. E. Mann, B. A. Thrush, D. R. Lide, J. J. Ball, and N. Acquista, J. Chem. Phys. 34, 420 (1961).
    [Crossref]
  6. S. Kimel, M. A. Hirshfeld, and J. H. Jaffe, J. Chem. Phys. 31, 81 (1959).
    [Crossref]
  7. A. Ben-Reuven, S. Kimel, M. A. Hirshfeld, and J. H. Jaffe, J. Chem. Phys. 35, 955 (1961).
    [Crossref]
  8. D. F. Smith and V. Anderson (private communication).
  9. W. F. Herget, N. M. Gailar, R. J. Lovell, and A. H. Nielsen, J. Opt. Soc. Am. 50, 1264 (1960).
    [Crossref]

1962 (1)

1961 (2)

D. E. Mann, B. A. Thrush, D. R. Lide, J. J. Ball, and N. Acquista, J. Chem. Phys. 34, 420 (1961).
[Crossref]

A. Ben-Reuven, S. Kimel, M. A. Hirshfeld, and J. H. Jaffe, J. Chem. Phys. 35, 955 (1961).
[Crossref]

1960 (1)

1959 (2)

S. Kimel, M. A. Hirshfeld, and J. H. Jaffe, J. Chem. Phys. 31, 81 (1959).
[Crossref]

D. F. Smith, J. Mol. Spectroscopy 3, 473 (1959).
[Crossref]

1958 (1)

G. A. Kuipers, J. Mol. Spectroscopy 2, 775 (1958).
[Crossref]

1956 (1)

W. S. Benedict, R. Herman, G. E. Moore, and S. Silverman, Can. J. Phys. 34, 850 (1956).
[Crossref]

Acquista, N.

D. E. Mann, B. A. Thrush, D. R. Lide, J. J. Ball, and N. Acquista, J. Chem. Phys. 34, 420 (1961).
[Crossref]

Anderson, V.

D. F. Smith and V. Anderson (private communication).

Ball, J. J.

D. E. Mann, B. A. Thrush, D. R. Lide, J. J. Ball, and N. Acquista, J. Chem. Phys. 34, 420 (1961).
[Crossref]

Benedict, W. S.

W. S. Benedict, R. Herman, G. E. Moore, and S. Silverman, Can. J. Phys. 34, 850 (1956).
[Crossref]

Ben-Reuven, A.

A. Ben-Reuven, S. Kimel, M. A. Hirshfeld, and J. H. Jaffe, J. Chem. Phys. 35, 955 (1961).
[Crossref]

Deeds, W. E.

Gailar, N. M.

Herget, W. F.

Herman, R.

W. S. Benedict, R. Herman, G. E. Moore, and S. Silverman, Can. J. Phys. 34, 850 (1956).
[Crossref]

Herndon, J. A.

Hirshfeld, M. A.

A. Ben-Reuven, S. Kimel, M. A. Hirshfeld, and J. H. Jaffe, J. Chem. Phys. 35, 955 (1961).
[Crossref]

S. Kimel, M. A. Hirshfeld, and J. H. Jaffe, J. Chem. Phys. 31, 81 (1959).
[Crossref]

Jaffe, J. H.

A. Ben-Reuven, S. Kimel, M. A. Hirshfeld, and J. H. Jaffe, J. Chem. Phys. 35, 955 (1961).
[Crossref]

S. Kimel, M. A. Hirshfeld, and J. H. Jaffe, J. Chem. Phys. 31, 81 (1959).
[Crossref]

Kimel, S.

A. Ben-Reuven, S. Kimel, M. A. Hirshfeld, and J. H. Jaffe, J. Chem. Phys. 35, 955 (1961).
[Crossref]

S. Kimel, M. A. Hirshfeld, and J. H. Jaffe, J. Chem. Phys. 31, 81 (1959).
[Crossref]

Kuipers, G. A.

G. A. Kuipers, J. Mol. Spectroscopy 2, 775 (1958).
[Crossref]

Lide, D. R.

D. E. Mann, B. A. Thrush, D. R. Lide, J. J. Ball, and N. Acquista, J. Chem. Phys. 34, 420 (1961).
[Crossref]

Lovell, R. J.

Mann, D. E.

D. E. Mann, B. A. Thrush, D. R. Lide, J. J. Ball, and N. Acquista, J. Chem. Phys. 34, 420 (1961).
[Crossref]

Moore, G. E.

W. S. Benedict, R. Herman, G. E. Moore, and S. Silverman, Can. J. Phys. 34, 850 (1956).
[Crossref]

Nielsen, A. H.

Silverman, S.

W. S. Benedict, R. Herman, G. E. Moore, and S. Silverman, Can. J. Phys. 34, 850 (1956).
[Crossref]

Smith, D. F.

D. F. Smith, J. Mol. Spectroscopy 3, 473 (1959).
[Crossref]

D. F. Smith and V. Anderson (private communication).

Thrush, B. A.

D. E. Mann, B. A. Thrush, D. R. Lide, J. J. Ball, and N. Acquista, J. Chem. Phys. 34, 420 (1961).
[Crossref]

Can. J. Phys. (1)

W. S. Benedict, R. Herman, G. E. Moore, and S. Silverman, Can. J. Phys. 34, 850 (1956).
[Crossref]

J. Chem. Phys. (3)

D. E. Mann, B. A. Thrush, D. R. Lide, J. J. Ball, and N. Acquista, J. Chem. Phys. 34, 420 (1961).
[Crossref]

S. Kimel, M. A. Hirshfeld, and J. H. Jaffe, J. Chem. Phys. 31, 81 (1959).
[Crossref]

A. Ben-Reuven, S. Kimel, M. A. Hirshfeld, and J. H. Jaffe, J. Chem. Phys. 35, 955 (1961).
[Crossref]

J. Mol. Spectroscopy (2)

G. A. Kuipers, J. Mol. Spectroscopy 2, 775 (1958).
[Crossref]

D. F. Smith, J. Mol. Spectroscopy 3, 473 (1959).
[Crossref]

J. Opt. Soc. Am. (2)

Other (1)

D. F. Smith and V. Anderson (private communication).

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Figures (9)

Fig. 1
Fig. 1

Pressure-induced line-center shifts for R(6) and R(2).

Fig. 2
Fig. 2

Line-center shift per unit pressure.

Fig. 3
Fig. 3

The R(6) line of CO normalized to unit area (the slit function).

Fig. 4
Fig. 4

Typical true and measured absorptance curves.

Fig. 5
Fig. 5

Some curves used in the procedure for correcting line shapes for the effects of instrumental broadening.

Fig. 6
Fig. 6

Plot of Δν/p vs |m|.

Fig. 7
Fig. 7

Dependence of Lorentz exponent η, on half-absorption half-width δν.

Fig. 8
Fig. 8

Observed and calculated line shapes for R(1) at 5-cm Hg pressure.

Fig. 9
Fig. 9

Observed and calculated line shapes for R(3) at 50-cm Hg pressure.

Tables (3)

Tables Icon

Table I Observed and calculated wavenumbers of the rotation lines in the (0–1) and (0–2) bands of HF.

Tables Icon

Table II Measured values of ν0, Bv, and Dv.

Tables Icon

Table III Measured values of the Lorentz parameters α0, η, and Δν for the rotational lines in the HF fundamental band.

Equations (12)

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ν m = k = 0 N c k m k ,
A ( ν ) = - S ( ν - ν ) a ( ν ) d ν ,
A ( ν m ) = S ( ν m - ν n ) a ( ν n )
A m = S m n a n .
( A m ) = ( S m n ) ( a n ) .
( a n ) = ( S m n ) - 1 ( A m ) .
α = α 0 ( Δ ν ) 2 [ ν - ν 0 η + ( Δ ν ) 2 ] - 1 .
T = e - α L ,
α i = α - m i [ α 0 m ( Δ ν m ) 2 ν - ν 0 m - 1.8 ] ,
[ ( α 0 - α ) / α ] 1 / η = ν ( Δ ν ) - 2 / η - ν 0 ( Δ ν ) - 2 / η .
ν - ν 0 ν - ν 0 ( α 0 - α α ) 1 / η
log [ ( α 0 - α ) / α ] = η log ν - ν 0 - 2 log Δ ν .