Abstract

The optical properties of an organic laser dye luminophor, Rhodamine B in ethanol, were investigated at both high and low concentrations as a function of temperature. At high concentrations the absorption spectra (extinction coefficient, k) and the refractive index (n) were determined by measuring the reflectivity of parallel-polarized light at the pseudo-Brewster angle at the dye–air interface. The absorption spectra at low concentration were also measured and compared with those at high concentration. It was found that at high concentration, independent of temperature, the dye–dye interaction among neighboring dye molecules contributes to the deviation of the absorption spectra from Beer’s law. The dependence of absorption spectral distribution on concentration becomes more pronounced as the solvent temperature is reduced. This is thought to be mainly due to the mutual interaction of neighboring molecules and also to the formation of higher-order aggregates. At low concentrations, as the temperature is reduced, the absorption spectra show little change and, in contrast to those at high concentration, obey the Beer–Lambert law; i.e., the absorption cross sections are independent of concentration. The absorption intensity of concentrated solutions decreases markedly compared with those at low concentrations.

© 1991 Optical Society of America

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References

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  1. W. C. Holmes, “Aggregation phenomena of Rhodamine dyes in aqueous solutions,” Ind. Eng. Chem. 16, 35 (1924).
    [CrossRef]
  2. L. V. Levshin and V. K. Gorskov, “Study of the nature of the bonding forces of associated dye molecules in concentrated solution,” Opt. Spectrosc. 10, 401–405 (1961).
  3. V. I. Permogorov, L. A. Serdyukova, and M. D. Frank, “The nature of the long-wavelength absorption and luminescence bands of dyes,” Opt. Spectrosc. 25, 38–42 (1968).
  4. J. E. Selwyn and J. I. Steinfeld, “Aggregation equilibria of xanthene dyes,” J. Phys. Chem. 76, 762–774 (1972).
    [CrossRef]
  5. M. Faraggi and D. Weinraub, “Solution properties of dye lasers. Rhodamine B in alcohols,” Chem. Phys. Lett. 103, 310–313 (1984).
    [CrossRef]
  6. L. V. Levshin and I. S. Lonskaya, “Dependence of the association of Rhodamines on the structure of their molecules and the nature of the solvent,” Opt. Spectrosc. 11, 148–150 (1961).
  7. L. V. Levshin, T. D. Slavnova, and V. I. Yuzhakov, “Spectroscopic manifestation of the association of Rhodamine 6G in alcoholic solutions,” Zh. Prikl. Spektrosk. 24, 985–990 (1976).
  8. Y. Lu and A. Penzkofer, “Absorption behavior of methanolic Rhodamine 6G solutions at high concentration,” Chem. Phys. 107, 175–184 (1986).
    [CrossRef]
  9. A. Penzkofer and Y. Lu, “Fluorescence quenching of Rhodamine 6G in methanol at high concentration,” Chem. Phys. 103, 399–405 (1986).
    [CrossRef]
  10. A. Penzkofer, W. Leupacher, and B. Meier, “Concentration-dependent absorption and emission behavior of a pyrimidone-carbocyanine dye in Hexafluoroisopropanol,” Chem. Phys. 115, 143–150 (1986).
    [CrossRef]
  11. S. P. F. Humphreys-Owen, “Comparison of reflection methods for measuring optical constants without polarimetric analysis,” Proc. Phys. Soc. London 77, 949–957 (1961).
    [CrossRef]
  12. K. H. Drexhage, in Dye Lasers, F. P. Schafer, ed. (Springer-Verlag, Berlin, 1977).
  13. A. Penzkofer and W. Leupacher, “Fluorescence behavior of highly concentrated Rhodamine 6G solutions,” J. Lumin. 37, 61–72 (1987).
    [CrossRef]
  14. M. A. Ali, J. Moghaddasi, and S. A. Ahmed, “Examination of temperature effects on the lasing characteristics of Rhodamine cw dye lasers,” Appl. Opt. 29, 3945–3949 (1990).
    [CrossRef] [PubMed]

1990 (1)

1987 (1)

A. Penzkofer and W. Leupacher, “Fluorescence behavior of highly concentrated Rhodamine 6G solutions,” J. Lumin. 37, 61–72 (1987).
[CrossRef]

1986 (3)

Y. Lu and A. Penzkofer, “Absorption behavior of methanolic Rhodamine 6G solutions at high concentration,” Chem. Phys. 107, 175–184 (1986).
[CrossRef]

A. Penzkofer and Y. Lu, “Fluorescence quenching of Rhodamine 6G in methanol at high concentration,” Chem. Phys. 103, 399–405 (1986).
[CrossRef]

A. Penzkofer, W. Leupacher, and B. Meier, “Concentration-dependent absorption and emission behavior of a pyrimidone-carbocyanine dye in Hexafluoroisopropanol,” Chem. Phys. 115, 143–150 (1986).
[CrossRef]

1984 (1)

M. Faraggi and D. Weinraub, “Solution properties of dye lasers. Rhodamine B in alcohols,” Chem. Phys. Lett. 103, 310–313 (1984).
[CrossRef]

1976 (1)

L. V. Levshin, T. D. Slavnova, and V. I. Yuzhakov, “Spectroscopic manifestation of the association of Rhodamine 6G in alcoholic solutions,” Zh. Prikl. Spektrosk. 24, 985–990 (1976).

1972 (1)

J. E. Selwyn and J. I. Steinfeld, “Aggregation equilibria of xanthene dyes,” J. Phys. Chem. 76, 762–774 (1972).
[CrossRef]

1968 (1)

V. I. Permogorov, L. A. Serdyukova, and M. D. Frank, “The nature of the long-wavelength absorption and luminescence bands of dyes,” Opt. Spectrosc. 25, 38–42 (1968).

1961 (3)

L. V. Levshin and V. K. Gorskov, “Study of the nature of the bonding forces of associated dye molecules in concentrated solution,” Opt. Spectrosc. 10, 401–405 (1961).

S. P. F. Humphreys-Owen, “Comparison of reflection methods for measuring optical constants without polarimetric analysis,” Proc. Phys. Soc. London 77, 949–957 (1961).
[CrossRef]

L. V. Levshin and I. S. Lonskaya, “Dependence of the association of Rhodamines on the structure of their molecules and the nature of the solvent,” Opt. Spectrosc. 11, 148–150 (1961).

1924 (1)

W. C. Holmes, “Aggregation phenomena of Rhodamine dyes in aqueous solutions,” Ind. Eng. Chem. 16, 35 (1924).
[CrossRef]

Ahmed, S. A.

Ali, M. A.

Drexhage, K. H.

K. H. Drexhage, in Dye Lasers, F. P. Schafer, ed. (Springer-Verlag, Berlin, 1977).

Faraggi, M.

M. Faraggi and D. Weinraub, “Solution properties of dye lasers. Rhodamine B in alcohols,” Chem. Phys. Lett. 103, 310–313 (1984).
[CrossRef]

Frank, M. D.

V. I. Permogorov, L. A. Serdyukova, and M. D. Frank, “The nature of the long-wavelength absorption and luminescence bands of dyes,” Opt. Spectrosc. 25, 38–42 (1968).

Gorskov, V. K.

L. V. Levshin and V. K. Gorskov, “Study of the nature of the bonding forces of associated dye molecules in concentrated solution,” Opt. Spectrosc. 10, 401–405 (1961).

Holmes, W. C.

W. C. Holmes, “Aggregation phenomena of Rhodamine dyes in aqueous solutions,” Ind. Eng. Chem. 16, 35 (1924).
[CrossRef]

Humphreys-Owen, S. P. F.

S. P. F. Humphreys-Owen, “Comparison of reflection methods for measuring optical constants without polarimetric analysis,” Proc. Phys. Soc. London 77, 949–957 (1961).
[CrossRef]

Leupacher, W.

A. Penzkofer and W. Leupacher, “Fluorescence behavior of highly concentrated Rhodamine 6G solutions,” J. Lumin. 37, 61–72 (1987).
[CrossRef]

A. Penzkofer, W. Leupacher, and B. Meier, “Concentration-dependent absorption and emission behavior of a pyrimidone-carbocyanine dye in Hexafluoroisopropanol,” Chem. Phys. 115, 143–150 (1986).
[CrossRef]

Levshin, L. V.

L. V. Levshin, T. D. Slavnova, and V. I. Yuzhakov, “Spectroscopic manifestation of the association of Rhodamine 6G in alcoholic solutions,” Zh. Prikl. Spektrosk. 24, 985–990 (1976).

L. V. Levshin and I. S. Lonskaya, “Dependence of the association of Rhodamines on the structure of their molecules and the nature of the solvent,” Opt. Spectrosc. 11, 148–150 (1961).

L. V. Levshin and V. K. Gorskov, “Study of the nature of the bonding forces of associated dye molecules in concentrated solution,” Opt. Spectrosc. 10, 401–405 (1961).

Lonskaya, I. S.

L. V. Levshin and I. S. Lonskaya, “Dependence of the association of Rhodamines on the structure of their molecules and the nature of the solvent,” Opt. Spectrosc. 11, 148–150 (1961).

Lu, Y.

Y. Lu and A. Penzkofer, “Absorption behavior of methanolic Rhodamine 6G solutions at high concentration,” Chem. Phys. 107, 175–184 (1986).
[CrossRef]

A. Penzkofer and Y. Lu, “Fluorescence quenching of Rhodamine 6G in methanol at high concentration,” Chem. Phys. 103, 399–405 (1986).
[CrossRef]

Meier, B.

A. Penzkofer, W. Leupacher, and B. Meier, “Concentration-dependent absorption and emission behavior of a pyrimidone-carbocyanine dye in Hexafluoroisopropanol,” Chem. Phys. 115, 143–150 (1986).
[CrossRef]

Moghaddasi, J.

Penzkofer, A.

A. Penzkofer and W. Leupacher, “Fluorescence behavior of highly concentrated Rhodamine 6G solutions,” J. Lumin. 37, 61–72 (1987).
[CrossRef]

A. Penzkofer, W. Leupacher, and B. Meier, “Concentration-dependent absorption and emission behavior of a pyrimidone-carbocyanine dye in Hexafluoroisopropanol,” Chem. Phys. 115, 143–150 (1986).
[CrossRef]

Y. Lu and A. Penzkofer, “Absorption behavior of methanolic Rhodamine 6G solutions at high concentration,” Chem. Phys. 107, 175–184 (1986).
[CrossRef]

A. Penzkofer and Y. Lu, “Fluorescence quenching of Rhodamine 6G in methanol at high concentration,” Chem. Phys. 103, 399–405 (1986).
[CrossRef]

Permogorov, V. I.

V. I. Permogorov, L. A. Serdyukova, and M. D. Frank, “The nature of the long-wavelength absorption and luminescence bands of dyes,” Opt. Spectrosc. 25, 38–42 (1968).

Selwyn, J. E.

J. E. Selwyn and J. I. Steinfeld, “Aggregation equilibria of xanthene dyes,” J. Phys. Chem. 76, 762–774 (1972).
[CrossRef]

Serdyukova, L. A.

V. I. Permogorov, L. A. Serdyukova, and M. D. Frank, “The nature of the long-wavelength absorption and luminescence bands of dyes,” Opt. Spectrosc. 25, 38–42 (1968).

Slavnova, T. D.

L. V. Levshin, T. D. Slavnova, and V. I. Yuzhakov, “Spectroscopic manifestation of the association of Rhodamine 6G in alcoholic solutions,” Zh. Prikl. Spektrosk. 24, 985–990 (1976).

Steinfeld, J. I.

J. E. Selwyn and J. I. Steinfeld, “Aggregation equilibria of xanthene dyes,” J. Phys. Chem. 76, 762–774 (1972).
[CrossRef]

Weinraub, D.

M. Faraggi and D. Weinraub, “Solution properties of dye lasers. Rhodamine B in alcohols,” Chem. Phys. Lett. 103, 310–313 (1984).
[CrossRef]

Yuzhakov, V. I.

L. V. Levshin, T. D. Slavnova, and V. I. Yuzhakov, “Spectroscopic manifestation of the association of Rhodamine 6G in alcoholic solutions,” Zh. Prikl. Spektrosk. 24, 985–990 (1976).

Appl. Opt. (1)

Chem. Phys. (3)

Y. Lu and A. Penzkofer, “Absorption behavior of methanolic Rhodamine 6G solutions at high concentration,” Chem. Phys. 107, 175–184 (1986).
[CrossRef]

A. Penzkofer and Y. Lu, “Fluorescence quenching of Rhodamine 6G in methanol at high concentration,” Chem. Phys. 103, 399–405 (1986).
[CrossRef]

A. Penzkofer, W. Leupacher, and B. Meier, “Concentration-dependent absorption and emission behavior of a pyrimidone-carbocyanine dye in Hexafluoroisopropanol,” Chem. Phys. 115, 143–150 (1986).
[CrossRef]

Chem. Phys. Lett. (1)

M. Faraggi and D. Weinraub, “Solution properties of dye lasers. Rhodamine B in alcohols,” Chem. Phys. Lett. 103, 310–313 (1984).
[CrossRef]

Ind. Eng. Chem. (1)

W. C. Holmes, “Aggregation phenomena of Rhodamine dyes in aqueous solutions,” Ind. Eng. Chem. 16, 35 (1924).
[CrossRef]

J. Lumin. (1)

A. Penzkofer and W. Leupacher, “Fluorescence behavior of highly concentrated Rhodamine 6G solutions,” J. Lumin. 37, 61–72 (1987).
[CrossRef]

J. Phys. Chem. (1)

J. E. Selwyn and J. I. Steinfeld, “Aggregation equilibria of xanthene dyes,” J. Phys. Chem. 76, 762–774 (1972).
[CrossRef]

Opt. Spectrosc. (3)

L. V. Levshin and V. K. Gorskov, “Study of the nature of the bonding forces of associated dye molecules in concentrated solution,” Opt. Spectrosc. 10, 401–405 (1961).

V. I. Permogorov, L. A. Serdyukova, and M. D. Frank, “The nature of the long-wavelength absorption and luminescence bands of dyes,” Opt. Spectrosc. 25, 38–42 (1968).

L. V. Levshin and I. S. Lonskaya, “Dependence of the association of Rhodamines on the structure of their molecules and the nature of the solvent,” Opt. Spectrosc. 11, 148–150 (1961).

Proc. Phys. Soc. London (1)

S. P. F. Humphreys-Owen, “Comparison of reflection methods for measuring optical constants without polarimetric analysis,” Proc. Phys. Soc. London 77, 949–957 (1961).
[CrossRef]

Zh. Prikl. Spektrosk. (1)

L. V. Levshin, T. D. Slavnova, and V. I. Yuzhakov, “Spectroscopic manifestation of the association of Rhodamine 6G in alcoholic solutions,” Zh. Prikl. Spektrosk. 24, 985–990 (1976).

Other (1)

K. H. Drexhage, in Dye Lasers, F. P. Schafer, ed. (Springer-Verlag, Berlin, 1977).

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Figures (7)

Fig. 1
Fig. 1

Measured absorption spectra at a low concentration (2 × 10−5 mol/L) of a Rh B solution in ethanol: 1, 23°C; 2, −5°C; 3, −20°C; 4, −70°C.

Fig. 2
Fig. 2

Measured fluorescence spectra of a 2 × 10−5 mol/L Rh B solution in ethanol: solid curve, 23°C; dashed curve, −5°C; dotted curve, −20°C; dotted–dashed curve, −70°C.

Fig. 3
Fig. 3

Measured minimum parallel reflectivity at a pseudo-Brewster angle Rp,min(ϕpB) for 0.45 mol/L Rh B in ethanol: 1, 23°C; 2, −5°C; 3, −20°C; 4, −70°C.

Fig. 4
Fig. 4

Measured pseudo-Brewster angle versus wavelength: dashed line, ethanol; solid curves, 0.45 mol/L Rh B in ethanol. 1, 23°C, 2, −5°C; 3, −20°C; 4, −70°C.

Fig. 5
Fig. 5

Absolute refractive indices versus wavelength: dashed line, ethanol; solid curves, 0.45 mol/L Rh B in ethanol. 1, 23°C; 2, −5°C; 3, −20°C; 4, −70°C.

Fig. 6
Fig. 6

Extinction coefficient versus wavelength for 0.45 mol/L Rh B in ethanol: 1, 23°C; 2, −5°C; 3, −20°C; 4, −70°C.

Fig. 7
Fig. 7

Absorption spectra of solutions of Rh B in ethanol at −70°C: solid curve, 2 × 10−5 mol/L; curve with circles, 0.45 mol/L.

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