Abstract

Experimental details for the taking of infrared absorption spectra of thin solid layers at various temperatures are given and a method described for measurement of their thickness. An account of the preparation of suitable samples for reflection spectra is also included.

The spectra of the four ammonium halides at 20°C and −150°C have been obtained and the results interpreted in terms of their crystal structure. The data support the following symmetries for the ammonium ion in the low temperature form: (I) Td in ammonium chloride, (II) Vd in ammonium bromide, (III) Vd in ammonium iodide, and (IV) C3v or C3 in ammonium fluoride.

© 1951 Optical Society of America

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  1. R. S. Krishnan, Proc. Indian Acad. Sci. 26A, 432 (1947).
  2. R. S. Krishnan, Proc. Indian Acad. Sci. 27A, 321 (1948).
  3. E. L. Wagner and D. F. Hornig, J. Chem. Phys. 18, 296 (1950).
    [Crossref]
  4. E. L. Wagner and D. F. Hornig, J. Chem. Phys. 18, 305 (1950).
    [Crossref]
  5. R. S. Halford, J. Chem. Phys. 14, 8 (1946).
    [Crossref]
  6. G. Placzek, The Structure of Molecules (Blackie and Son, Ltd., London, 1932), p. 65.
  7. C. J. Brester, Z. Physik 24, 324 (1924).
    [Crossref]
  8. P. Niggli, Geometrische Kristallographie des Diskontinuums (Gebrueder Bornstraeger, Leipzig, 1919), pp. 404–411.
  9. S. Bhagavantam and T. Venkatarayudu, Proc. Indian Acad. Sci. 9A, 224 (1939).
  10. L. Couture and J. P. Mathieu, J. phys. et radium 10, 145 (1949).
    [Crossref]
  11. M. Born and M. Bradburn, Proc. Roy. Soc. (London) 188A, 161 (1947).
    [Crossref]
  12. H. M. J. Smith, Trans. Roy. Soc. (London) 241A, 105 (1948).
    [Crossref]
  13. D. F. Hornig, J. Chem. Phys. 16, 1063 (1948).
    [Crossref]
  14. L. F. H. Bovey, J. Opt. Soc. Am. 41, 381 (1951).
    [Crossref] [PubMed]
  15. O. Reinkober, Z. Physik. 5, 192 (1921).
    [Crossref]
  16. Conn, Lee, and Sutherland, Proc. Roy. Soc. (London) 176A, 484 (1940).
    [Crossref]
  17. R. Pohlmann, Z. Physik. 79, 394 (1932).
    [Crossref]
  18. L. Wilberg, Z. Physik. 64, 304 (1930).
    [Crossref]
  19. G. Herzberg, Infrared and Raman Spectra (D. Van Nostrand Company, Inc., New York, 1945).
  20. J. P. Mathieu, Spectre de Vibration et Symetrie des Molecules et des Cristaux (Hermann and Company, Paris, 1945).
  21. L. Couture and J. P. Mathieu, Proc. Indian Acad. Sci. 28A, 401 (1948).
  22. Bovey, Lee, and Sutherland, in preparation.
  23. L. F. H. Bovey, J. Chem. Phys. 18, 1684 (1950).
    [Crossref]
  24. R. W. G. Wyckoff, Crystal Structures (Interscience Publishers, Inc., New York1948).
  25. R. Ananthakrishnan, Proc. Indian Acad. Sci. 5A, 76 (1937).
  26. A. Smits and C. H. MacGillavry, Z. Physik. Chem. 166A, 97 (1933).
  27. J. A. A. Ketelaar, Nature 134, 250 (1934).
    [Crossref]
  28. J. Weigle and H. Saini, Helv. Phys. Acta. 9, 515 (1936).
  29. Smits, Ketelaar, and Muller, Z. Physik. Chem. A175, 359 (1936).
  30. Smits, Tollenaar, and Kroger, Z. Physik. Chem. B41, 215 (1938).
  31. G. Bartlett and I. Langmuir, J. Am. Chem. Soc. 43, 84 (1921).
    [Crossref]
  32. Simon, Simson, and Ruhemann, Z. Physik. Chem. 129, 339 (1927).
  33. A. Smits and G. J. Muller, Z. Physik. Chem. 36B, 140 (1937).
  34. A. C. Menzies and H. R. Mills, Proc. Roy. Soc. (London) 148A, 407 (1935).
    [Crossref]
  35. W. Zachariasen, Z. Physik. Chem. 127, 218 (1927).
  36. D. J. Williams, Am. Chem. Soc. 64, 857 (1942).
    [Crossref]
  37. Recent work by Mathieu, Aguirre, and Couture-Mathieu, Compt. rend. 232, 318 (1951), on ammonium chloride at −100°C has shown a strong Raman line at 1717 cm−1 (Type E) which would seem to be the fundamental ν2.
  38. J. A. A. Ketelaar, Rec. Trav. Chim. 60, 523 (1941).

1951 (2)

L. F. H. Bovey, J. Opt. Soc. Am. 41, 381 (1951).
[Crossref] [PubMed]

Recent work by Mathieu, Aguirre, and Couture-Mathieu, Compt. rend. 232, 318 (1951), on ammonium chloride at −100°C has shown a strong Raman line at 1717 cm−1 (Type E) which would seem to be the fundamental ν2.

1950 (3)

L. F. H. Bovey, J. Chem. Phys. 18, 1684 (1950).
[Crossref]

E. L. Wagner and D. F. Hornig, J. Chem. Phys. 18, 296 (1950).
[Crossref]

E. L. Wagner and D. F. Hornig, J. Chem. Phys. 18, 305 (1950).
[Crossref]

1949 (1)

L. Couture and J. P. Mathieu, J. phys. et radium 10, 145 (1949).
[Crossref]

1948 (4)

R. S. Krishnan, Proc. Indian Acad. Sci. 27A, 321 (1948).

H. M. J. Smith, Trans. Roy. Soc. (London) 241A, 105 (1948).
[Crossref]

D. F. Hornig, J. Chem. Phys. 16, 1063 (1948).
[Crossref]

L. Couture and J. P. Mathieu, Proc. Indian Acad. Sci. 28A, 401 (1948).

1947 (2)

R. S. Krishnan, Proc. Indian Acad. Sci. 26A, 432 (1947).

M. Born and M. Bradburn, Proc. Roy. Soc. (London) 188A, 161 (1947).
[Crossref]

1946 (1)

R. S. Halford, J. Chem. Phys. 14, 8 (1946).
[Crossref]

1942 (1)

D. J. Williams, Am. Chem. Soc. 64, 857 (1942).
[Crossref]

1941 (1)

J. A. A. Ketelaar, Rec. Trav. Chim. 60, 523 (1941).

1940 (1)

Conn, Lee, and Sutherland, Proc. Roy. Soc. (London) 176A, 484 (1940).
[Crossref]

1939 (1)

S. Bhagavantam and T. Venkatarayudu, Proc. Indian Acad. Sci. 9A, 224 (1939).

1938 (1)

Smits, Tollenaar, and Kroger, Z. Physik. Chem. B41, 215 (1938).

1937 (2)

R. Ananthakrishnan, Proc. Indian Acad. Sci. 5A, 76 (1937).

A. Smits and G. J. Muller, Z. Physik. Chem. 36B, 140 (1937).

1936 (2)

J. Weigle and H. Saini, Helv. Phys. Acta. 9, 515 (1936).

Smits, Ketelaar, and Muller, Z. Physik. Chem. A175, 359 (1936).

1935 (1)

A. C. Menzies and H. R. Mills, Proc. Roy. Soc. (London) 148A, 407 (1935).
[Crossref]

1934 (1)

J. A. A. Ketelaar, Nature 134, 250 (1934).
[Crossref]

1933 (1)

A. Smits and C. H. MacGillavry, Z. Physik. Chem. 166A, 97 (1933).

1932 (1)

R. Pohlmann, Z. Physik. 79, 394 (1932).
[Crossref]

1930 (1)

L. Wilberg, Z. Physik. 64, 304 (1930).
[Crossref]

1927 (2)

Simon, Simson, and Ruhemann, Z. Physik. Chem. 129, 339 (1927).

W. Zachariasen, Z. Physik. Chem. 127, 218 (1927).

1924 (1)

C. J. Brester, Z. Physik 24, 324 (1924).
[Crossref]

1921 (2)

O. Reinkober, Z. Physik. 5, 192 (1921).
[Crossref]

G. Bartlett and I. Langmuir, J. Am. Chem. Soc. 43, 84 (1921).
[Crossref]

Aguirre,

Recent work by Mathieu, Aguirre, and Couture-Mathieu, Compt. rend. 232, 318 (1951), on ammonium chloride at −100°C has shown a strong Raman line at 1717 cm−1 (Type E) which would seem to be the fundamental ν2.

Ananthakrishnan, R.

R. Ananthakrishnan, Proc. Indian Acad. Sci. 5A, 76 (1937).

Bartlett, G.

G. Bartlett and I. Langmuir, J. Am. Chem. Soc. 43, 84 (1921).
[Crossref]

Bhagavantam, S.

S. Bhagavantam and T. Venkatarayudu, Proc. Indian Acad. Sci. 9A, 224 (1939).

Born, M.

M. Born and M. Bradburn, Proc. Roy. Soc. (London) 188A, 161 (1947).
[Crossref]

Bovey,

Bovey, Lee, and Sutherland, in preparation.

Bovey, L. F. H.

Bradburn, M.

M. Born and M. Bradburn, Proc. Roy. Soc. (London) 188A, 161 (1947).
[Crossref]

Brester, C. J.

C. J. Brester, Z. Physik 24, 324 (1924).
[Crossref]

Conn,

Conn, Lee, and Sutherland, Proc. Roy. Soc. (London) 176A, 484 (1940).
[Crossref]

Couture, L.

L. Couture and J. P. Mathieu, J. phys. et radium 10, 145 (1949).
[Crossref]

L. Couture and J. P. Mathieu, Proc. Indian Acad. Sci. 28A, 401 (1948).

Couture-Mathieu,

Recent work by Mathieu, Aguirre, and Couture-Mathieu, Compt. rend. 232, 318 (1951), on ammonium chloride at −100°C has shown a strong Raman line at 1717 cm−1 (Type E) which would seem to be the fundamental ν2.

Halford, R. S.

R. S. Halford, J. Chem. Phys. 14, 8 (1946).
[Crossref]

Herzberg, G.

G. Herzberg, Infrared and Raman Spectra (D. Van Nostrand Company, Inc., New York, 1945).

Hornig, D. F.

E. L. Wagner and D. F. Hornig, J. Chem. Phys. 18, 305 (1950).
[Crossref]

E. L. Wagner and D. F. Hornig, J. Chem. Phys. 18, 296 (1950).
[Crossref]

D. F. Hornig, J. Chem. Phys. 16, 1063 (1948).
[Crossref]

Ketelaar,

Smits, Ketelaar, and Muller, Z. Physik. Chem. A175, 359 (1936).

Ketelaar, J. A. A.

J. A. A. Ketelaar, Rec. Trav. Chim. 60, 523 (1941).

J. A. A. Ketelaar, Nature 134, 250 (1934).
[Crossref]

Krishnan, R. S.

R. S. Krishnan, Proc. Indian Acad. Sci. 27A, 321 (1948).

R. S. Krishnan, Proc. Indian Acad. Sci. 26A, 432 (1947).

Kroger,

Smits, Tollenaar, and Kroger, Z. Physik. Chem. B41, 215 (1938).

Langmuir, I.

G. Bartlett and I. Langmuir, J. Am. Chem. Soc. 43, 84 (1921).
[Crossref]

Lee,

Conn, Lee, and Sutherland, Proc. Roy. Soc. (London) 176A, 484 (1940).
[Crossref]

Bovey, Lee, and Sutherland, in preparation.

MacGillavry, C. H.

A. Smits and C. H. MacGillavry, Z. Physik. Chem. 166A, 97 (1933).

Mathieu,

Recent work by Mathieu, Aguirre, and Couture-Mathieu, Compt. rend. 232, 318 (1951), on ammonium chloride at −100°C has shown a strong Raman line at 1717 cm−1 (Type E) which would seem to be the fundamental ν2.

Mathieu, J. P.

L. Couture and J. P. Mathieu, J. phys. et radium 10, 145 (1949).
[Crossref]

L. Couture and J. P. Mathieu, Proc. Indian Acad. Sci. 28A, 401 (1948).

J. P. Mathieu, Spectre de Vibration et Symetrie des Molecules et des Cristaux (Hermann and Company, Paris, 1945).

Menzies, A. C.

A. C. Menzies and H. R. Mills, Proc. Roy. Soc. (London) 148A, 407 (1935).
[Crossref]

Mills, H. R.

A. C. Menzies and H. R. Mills, Proc. Roy. Soc. (London) 148A, 407 (1935).
[Crossref]

Muller,

Smits, Ketelaar, and Muller, Z. Physik. Chem. A175, 359 (1936).

Muller, G. J.

A. Smits and G. J. Muller, Z. Physik. Chem. 36B, 140 (1937).

Niggli, P.

P. Niggli, Geometrische Kristallographie des Diskontinuums (Gebrueder Bornstraeger, Leipzig, 1919), pp. 404–411.

Placzek, G.

G. Placzek, The Structure of Molecules (Blackie and Son, Ltd., London, 1932), p. 65.

Pohlmann, R.

R. Pohlmann, Z. Physik. 79, 394 (1932).
[Crossref]

Reinkober, O.

O. Reinkober, Z. Physik. 5, 192 (1921).
[Crossref]

Ruhemann,

Simon, Simson, and Ruhemann, Z. Physik. Chem. 129, 339 (1927).

Saini, H.

J. Weigle and H. Saini, Helv. Phys. Acta. 9, 515 (1936).

Simon,

Simon, Simson, and Ruhemann, Z. Physik. Chem. 129, 339 (1927).

Simson,

Simon, Simson, and Ruhemann, Z. Physik. Chem. 129, 339 (1927).

Smith, H. M. J.

H. M. J. Smith, Trans. Roy. Soc. (London) 241A, 105 (1948).
[Crossref]

Smits,

Smits, Tollenaar, and Kroger, Z. Physik. Chem. B41, 215 (1938).

Smits, Ketelaar, and Muller, Z. Physik. Chem. A175, 359 (1936).

Smits, A.

A. Smits and G. J. Muller, Z. Physik. Chem. 36B, 140 (1937).

A. Smits and C. H. MacGillavry, Z. Physik. Chem. 166A, 97 (1933).

Sutherland,

Conn, Lee, and Sutherland, Proc. Roy. Soc. (London) 176A, 484 (1940).
[Crossref]

Bovey, Lee, and Sutherland, in preparation.

Tollenaar,

Smits, Tollenaar, and Kroger, Z. Physik. Chem. B41, 215 (1938).

Venkatarayudu, T.

S. Bhagavantam and T. Venkatarayudu, Proc. Indian Acad. Sci. 9A, 224 (1939).

Wagner, E. L.

E. L. Wagner and D. F. Hornig, J. Chem. Phys. 18, 296 (1950).
[Crossref]

E. L. Wagner and D. F. Hornig, J. Chem. Phys. 18, 305 (1950).
[Crossref]

Weigle, J.

J. Weigle and H. Saini, Helv. Phys. Acta. 9, 515 (1936).

Wilberg, L.

L. Wilberg, Z. Physik. 64, 304 (1930).
[Crossref]

Williams, D. J.

D. J. Williams, Am. Chem. Soc. 64, 857 (1942).
[Crossref]

Wyckoff, R. W. G.

R. W. G. Wyckoff, Crystal Structures (Interscience Publishers, Inc., New York1948).

Zachariasen, W.

W. Zachariasen, Z. Physik. Chem. 127, 218 (1927).

Am. Chem. Soc. (1)

D. J. Williams, Am. Chem. Soc. 64, 857 (1942).
[Crossref]

Compt. rend. (1)

Recent work by Mathieu, Aguirre, and Couture-Mathieu, Compt. rend. 232, 318 (1951), on ammonium chloride at −100°C has shown a strong Raman line at 1717 cm−1 (Type E) which would seem to be the fundamental ν2.

Helv. Phys. Acta. (1)

J. Weigle and H. Saini, Helv. Phys. Acta. 9, 515 (1936).

J. Am. Chem. Soc. (1)

G. Bartlett and I. Langmuir, J. Am. Chem. Soc. 43, 84 (1921).
[Crossref]

J. Chem. Phys. (5)

L. F. H. Bovey, J. Chem. Phys. 18, 1684 (1950).
[Crossref]

E. L. Wagner and D. F. Hornig, J. Chem. Phys. 18, 296 (1950).
[Crossref]

E. L. Wagner and D. F. Hornig, J. Chem. Phys. 18, 305 (1950).
[Crossref]

R. S. Halford, J. Chem. Phys. 14, 8 (1946).
[Crossref]

D. F. Hornig, J. Chem. Phys. 16, 1063 (1948).
[Crossref]

J. Opt. Soc. Am. (1)

J. phys. et radium (1)

L. Couture and J. P. Mathieu, J. phys. et radium 10, 145 (1949).
[Crossref]

Nature (1)

J. A. A. Ketelaar, Nature 134, 250 (1934).
[Crossref]

Proc. Indian Acad. Sci. (5)

S. Bhagavantam and T. Venkatarayudu, Proc. Indian Acad. Sci. 9A, 224 (1939).

R. Ananthakrishnan, Proc. Indian Acad. Sci. 5A, 76 (1937).

L. Couture and J. P. Mathieu, Proc. Indian Acad. Sci. 28A, 401 (1948).

R. S. Krishnan, Proc. Indian Acad. Sci. 26A, 432 (1947).

R. S. Krishnan, Proc. Indian Acad. Sci. 27A, 321 (1948).

Proc. Roy. Soc. (London) (3)

M. Born and M. Bradburn, Proc. Roy. Soc. (London) 188A, 161 (1947).
[Crossref]

Conn, Lee, and Sutherland, Proc. Roy. Soc. (London) 176A, 484 (1940).
[Crossref]

A. C. Menzies and H. R. Mills, Proc. Roy. Soc. (London) 148A, 407 (1935).
[Crossref]

Rec. Trav. Chim. (1)

J. A. A. Ketelaar, Rec. Trav. Chim. 60, 523 (1941).

Trans. Roy. Soc. (London) (1)

H. M. J. Smith, Trans. Roy. Soc. (London) 241A, 105 (1948).
[Crossref]

Z. Physik (1)

C. J. Brester, Z. Physik 24, 324 (1924).
[Crossref]

Z. Physik. (3)

O. Reinkober, Z. Physik. 5, 192 (1921).
[Crossref]

R. Pohlmann, Z. Physik. 79, 394 (1932).
[Crossref]

L. Wilberg, Z. Physik. 64, 304 (1930).
[Crossref]

Z. Physik. Chem. (6)

W. Zachariasen, Z. Physik. Chem. 127, 218 (1927).

Simon, Simson, and Ruhemann, Z. Physik. Chem. 129, 339 (1927).

A. Smits and G. J. Muller, Z. Physik. Chem. 36B, 140 (1937).

Smits, Ketelaar, and Muller, Z. Physik. Chem. A175, 359 (1936).

Smits, Tollenaar, and Kroger, Z. Physik. Chem. B41, 215 (1938).

A. Smits and C. H. MacGillavry, Z. Physik. Chem. 166A, 97 (1933).

Other (6)

Bovey, Lee, and Sutherland, in preparation.

R. W. G. Wyckoff, Crystal Structures (Interscience Publishers, Inc., New York1948).

G. Herzberg, Infrared and Raman Spectra (D. Van Nostrand Company, Inc., New York, 1945).

J. P. Mathieu, Spectre de Vibration et Symetrie des Molecules et des Cristaux (Hermann and Company, Paris, 1945).

P. Niggli, Geometrische Kristallographie des Diskontinuums (Gebrueder Bornstraeger, Leipzig, 1919), pp. 404–411.

G. Placzek, The Structure of Molecules (Blackie and Son, Ltd., London, 1932), p. 65.

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Figures (8)

Fig. 1
Fig. 1

Photograph of adaptation to Michelson interferometer with which thickness of thin films can be measured. The sample holder is shown in position. The stainless steel mirror, on which the layer is sublimed, replaces the usual fixed mirror of the interferometer.

Fig. 2
Fig. 2

Absorption spectrum of NH4Cl (for approximately 3μ thickness).

Fig. 3
Fig. 3

Absorption spectrum of NH4Br (for approximately 4μ thickness).

Fig. 4
Fig. 4

Absorption spectrum of NH4I (for approximately 3μ thickness).

Fig. 5
Fig. 5

Absorption spectrum for NH4F.

Fig. 6
Fig. 6

Reflection spectra of ammonium chloride and bromide. Different energy scales are used for the 3.2μ and 7μ regions.

Fig. 7
Fig. 7

Reflection spectra of ammonium iodide and fluoride.

Fig. 8
Fig. 8

Unit cell of ammonium fluoride.

Tables (7)

Tables Icon

Table I Selection rules for vibration of XY4 molecule of certain symmetries.

Tables Icon

Table II Infrared and Raman lines of NH4Cl at 20°C.

Tables Icon

Table III Infrared and Raman lines of NH4Cl at low temperatures.

Tables Icon

Table IV Infrared and Raman lines of NH4Br at 20°C.

Tables Icon

Table V Infrared and Raman lines of NH4Br at low temperatures.

Tables Icon

Table VI Infrared and Raman lines of NH4I.

Tables Icon

Table VII Infrared and Raman lines of NH4F.