Abstract

The first observation to our knowledge of a second-order nonlinear optical effect in a nonpolar molecular ion is reported. Hyper-Rayleigh scattering was observed from aqueous and organic solutions of the tricyanomethanide ion [C(CN)3]. Because of the absence of a dipole moment and the presence of a charge in this planar, nonpolar, but highly polarizable molecular anion with D3h symmetry, no electric-field-induced second-harmonic-generation experiments are possible. The experimental values for the first hyperpolarizability βxxx [(7 ± 1.5) × 10−30 esu, independent of the solvent] are in good agreement with the results from quantum-chemical calculations.

© 1993 Optical Society of America

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    [CrossRef]

1992 (2)

J. L. Brédas, F. Meyers, B. M. Pierce, J. Zyss, J. Am. Chem. Soc. 114, 4928 (1992).
[CrossRef]

K. Clays, A. Persoons, Rev. Sci. Instrum. 63, 3285 (1992).
[CrossRef]

1991 (2)

J. Zyss, Nonlinear Opt. 1, 3 (1991).

K. Clays, A. Persoons, Phys. Rev. Lett. 66, 2980 (1991).
[CrossRef] [PubMed]

1990 (1)

H. A. Kurtz, J. J. P. Stewart, K. M. Dieter, J. Comput. Chem. 11, 82 (1990).
[CrossRef]

1989 (1)

B. M. Pierce, J. Chem. Phys. 91, 791 (1989).
[CrossRef]

1984 (1)

D. J. Williams, Angew. Chem. Int. Ed. Engl. 23, 690 (1984).
[CrossRef]

1970 (1)

P. D. Maker, Phys. Rev. A 1, 923 (1970).
[CrossRef]

1967 (1)

P. Andersen, B. Klewe, E. Thom, Acta Chem. Scand. 21, 1530 (1967).
[CrossRef]

1966 (1)

R. Bersohn, Y.-H. Pao, M. L. Frisch, J. Chem. Phys. 45, 3184 (1966).
[CrossRef]

1965 (2)

S. J. Cyvin, J. E. Rauch, J. C. Decius, J. Chem. Phys. 43, 4083 (1965).
[CrossRef]

R. W. Terhune, P. D. Maker, C. M. Savage, Phys. Rev. Lett. 14, 681 (1965).
[CrossRef]

1963 (2)

P. Anderson, B. Klewe, Nature 200, 464 (1963).
[CrossRef]

F. A. Miller, W. K. Baer, Spectrochim. Acta 19, 73 (1963).
[CrossRef]

1962 (2)

D. A. Long, R. A. G. Carrington, R. B. Gravenor, Nature 196, 371 (1962).
[CrossRef]

S. Trofimenko, E. L. Little, H. F. Mower, J. Org. Chem. 27, 433 (1962).
[CrossRef]

Andersen, P.

P. Andersen, B. Klewe, E. Thom, Acta Chem. Scand. 21, 1530 (1967).
[CrossRef]

Anderson, P.

P. Anderson, B. Klewe, Nature 200, 464 (1963).
[CrossRef]

Baer, W. K.

F. A. Miller, W. K. Baer, Spectrochim. Acta 19, 73 (1963).
[CrossRef]

Bersohn, R.

R. Bersohn, Y.-H. Pao, M. L. Frisch, J. Chem. Phys. 45, 3184 (1966).
[CrossRef]

Brédas, J. L.

J. L. Brédas, F. Meyers, B. M. Pierce, J. Zyss, J. Am. Chem. Soc. 114, 4928 (1992).
[CrossRef]

Carrington, R. A. G.

D. A. Long, R. A. G. Carrington, R. B. Gravenor, Nature 196, 371 (1962).
[CrossRef]

Clays, K.

K. Clays, A. Persoons, Rev. Sci. Instrum. 63, 3285 (1992).
[CrossRef]

K. Clays, A. Persoons, Phys. Rev. Lett. 66, 2980 (1991).
[CrossRef] [PubMed]

Cyvin, S. J.

S. J. Cyvin, J. E. Rauch, J. C. Decius, J. Chem. Phys. 43, 4083 (1965).
[CrossRef]

Decius, J. C.

S. J. Cyvin, J. E. Rauch, J. C. Decius, J. Chem. Phys. 43, 4083 (1965).
[CrossRef]

Dieter, K. M.

H. A. Kurtz, J. J. P. Stewart, K. M. Dieter, J. Comput. Chem. 11, 82 (1990).
[CrossRef]

Frisch, M. L.

R. Bersohn, Y.-H. Pao, M. L. Frisch, J. Chem. Phys. 45, 3184 (1966).
[CrossRef]

Gravenor, R. B.

D. A. Long, R. A. G. Carrington, R. B. Gravenor, Nature 196, 371 (1962).
[CrossRef]

Klewe, B.

P. Andersen, B. Klewe, E. Thom, Acta Chem. Scand. 21, 1530 (1967).
[CrossRef]

P. Anderson, B. Klewe, Nature 200, 464 (1963).
[CrossRef]

Kurtz, H. A.

H. A. Kurtz, J. J. P. Stewart, K. M. Dieter, J. Comput. Chem. 11, 82 (1990).
[CrossRef]

Little, E. L.

S. Trofimenko, E. L. Little, H. F. Mower, J. Org. Chem. 27, 433 (1962).
[CrossRef]

Long, D. A.

D. A. Long, R. A. G. Carrington, R. B. Gravenor, Nature 196, 371 (1962).
[CrossRef]

Maker, P. D.

P. D. Maker, Phys. Rev. A 1, 923 (1970).
[CrossRef]

R. W. Terhune, P. D. Maker, C. M. Savage, Phys. Rev. Lett. 14, 681 (1965).
[CrossRef]

Meyers, F.

J. L. Brédas, F. Meyers, B. M. Pierce, J. Zyss, J. Am. Chem. Soc. 114, 4928 (1992).
[CrossRef]

Miller, F. A.

F. A. Miller, W. K. Baer, Spectrochim. Acta 19, 73 (1963).
[CrossRef]

Mower, H. F.

S. Trofimenko, E. L. Little, H. F. Mower, J. Org. Chem. 27, 433 (1962).
[CrossRef]

Pao, Y.-H.

R. Bersohn, Y.-H. Pao, M. L. Frisch, J. Chem. Phys. 45, 3184 (1966).
[CrossRef]

Persoons, A.

K. Clays, A. Persoons, Rev. Sci. Instrum. 63, 3285 (1992).
[CrossRef]

K. Clays, A. Persoons, Phys. Rev. Lett. 66, 2980 (1991).
[CrossRef] [PubMed]

Pierce, B. M.

J. L. Brédas, F. Meyers, B. M. Pierce, J. Zyss, J. Am. Chem. Soc. 114, 4928 (1992).
[CrossRef]

B. M. Pierce, J. Chem. Phys. 91, 791 (1989).
[CrossRef]

Rauch, J. E.

S. J. Cyvin, J. E. Rauch, J. C. Decius, J. Chem. Phys. 43, 4083 (1965).
[CrossRef]

Savage, C. M.

R. W. Terhune, P. D. Maker, C. M. Savage, Phys. Rev. Lett. 14, 681 (1965).
[CrossRef]

Stewart, J. J. P.

H. A. Kurtz, J. J. P. Stewart, K. M. Dieter, J. Comput. Chem. 11, 82 (1990).
[CrossRef]

Terhune, R. W.

R. W. Terhune, P. D. Maker, C. M. Savage, Phys. Rev. Lett. 14, 681 (1965).
[CrossRef]

Thom, E.

P. Andersen, B. Klewe, E. Thom, Acta Chem. Scand. 21, 1530 (1967).
[CrossRef]

Trofimenko, S.

S. Trofimenko, E. L. Little, H. F. Mower, J. Org. Chem. 27, 433 (1962).
[CrossRef]

Williams, D. J.

D. J. Williams, Angew. Chem. Int. Ed. Engl. 23, 690 (1984).
[CrossRef]

Zyss, J.

J. L. Brédas, F. Meyers, B. M. Pierce, J. Zyss, J. Am. Chem. Soc. 114, 4928 (1992).
[CrossRef]

J. Zyss, Nonlinear Opt. 1, 3 (1991).

Acta Chem. Scand. (1)

P. Andersen, B. Klewe, E. Thom, Acta Chem. Scand. 21, 1530 (1967).
[CrossRef]

Angew. Chem. Int. Ed. Engl. (1)

D. J. Williams, Angew. Chem. Int. Ed. Engl. 23, 690 (1984).
[CrossRef]

J. Am. Chem. Soc. (1)

J. L. Brédas, F. Meyers, B. M. Pierce, J. Zyss, J. Am. Chem. Soc. 114, 4928 (1992).
[CrossRef]

J. Chem. Phys. (3)

R. Bersohn, Y.-H. Pao, M. L. Frisch, J. Chem. Phys. 45, 3184 (1966).
[CrossRef]

S. J. Cyvin, J. E. Rauch, J. C. Decius, J. Chem. Phys. 43, 4083 (1965).
[CrossRef]

B. M. Pierce, J. Chem. Phys. 91, 791 (1989).
[CrossRef]

J. Comput. Chem. (1)

H. A. Kurtz, J. J. P. Stewart, K. M. Dieter, J. Comput. Chem. 11, 82 (1990).
[CrossRef]

J. Org. Chem. (1)

S. Trofimenko, E. L. Little, H. F. Mower, J. Org. Chem. 27, 433 (1962).
[CrossRef]

Nature (2)

P. Anderson, B. Klewe, Nature 200, 464 (1963).
[CrossRef]

D. A. Long, R. A. G. Carrington, R. B. Gravenor, Nature 196, 371 (1962).
[CrossRef]

Nonlinear Opt. (1)

J. Zyss, Nonlinear Opt. 1, 3 (1991).

Phys. Rev. A (1)

P. D. Maker, Phys. Rev. A 1, 923 (1970).
[CrossRef]

Phys. Rev. Lett. (2)

K. Clays, A. Persoons, Phys. Rev. Lett. 66, 2980 (1991).
[CrossRef] [PubMed]

R. W. Terhune, P. D. Maker, C. M. Savage, Phys. Rev. Lett. 14, 681 (1965).
[CrossRef]

Rev. Sci. Instrum. (1)

K. Clays, A. Persoons, Rev. Sci. Instrum. 63, 3285 (1992).
[CrossRef]

Spectrochim. Acta (1)

F. A. Miller, W. K. Baer, Spectrochim. Acta 19, 73 (1963).
[CrossRef]

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Figures (2)

Fig. 1
Fig. 1

Molecular structure and definition of molecular coordinates for the octopolar tricyanomethanide anion [C(CN3)], together with a pictorial representation of the charge transfers in the two excited states that provide the most significant contributions to the first hyperpolarizability β. The plus (minus) represents a decrease (increase) in the π electron charge.

Fig. 2
Fig. 2

Quadratic coefficient I(2ω)/I2(ω) versus Ns, the number density of tricyanomethanide in methanol at 293 K.

Tables (1)

Tables Icon

Table 1 Experimental and Calculated Values of β for Tricyanomethanide Iona

Equations (4)

Equations on this page are rendered with MathJax. Learn more.

μ i = α i j · E j + β i j k · · E j E k + ,
P i ( 2 ω ) = B i j k · · E j ( ω ) E k ( ω ) ,
I J ( 2 ω ) = G B J Z Z 2 I Z 2 ( ω ) ,
B J Z Z 2 = F ω 4 F 2 ω 2 ( N S B J Z Z 2 s + N S B J Z Z 2 s ) ,

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