Commissariat à l’Energie Atomique, Institut de Recherche et de Developpement Industriel, Departement d’Electronique et d’Instrumentation Nucléaire, Laboratoire d’Etudes et de Recherches Avancées, 91191 Gif-sur-Yvette Cedex, France
F. Kajzar and J. Messier, "Cubic hyperpolarizabilities and local electric field in alkanes and substituted alkanes," J. Opt. Soc. Am. B 4, 1040-1046 (1987)
Cubic hyperpolarizability of a family of alkanes and substituted alkanes with a general formula CH3–(CH2)n−2CH2X (6 ≤ n ≤ 16 and X = H, Cl, Br, I) was measured by using third-harmonic generation at 1.064 μm. Using an additivity model and Onsager’s formulas for local-field factors, the cubic hyperpolarizabilities of the and –CH2X groups were determined, and the following values were obtained (in 10−37 esu): γCH2 = 6.6, γCH2X = 5.2 (X = H), 9.3 (X = Cl), 18.3 (X = Br), and 41.4 (X = I). For C–X bonds the corresponding values are γC–H = 2, γC–C = 1.2, γC–C = 7.7, γC–Br = 13.6, and γC–H = 30.6. A comparison of the above values with those found for other organic solvents shows the importance of molecular geometry in the additivity model.
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Coherence Length, Refractive-Index Dispersion, and Cubic Susceptibilities for Studied Alkanes and Substituted Alkanes at 1.064 μm and at Room Temperature (20°C)a
The precision in coherence-length determination is better than 1% and the relative precision in χ(3) better than 2%.
10−14 esu = 1.4 × 10−22 MKSA (SI units).
Table 3
Group Hyperpolarizabilities (in 10−37 esu)a for Studied Alkanes and Alkane Derivatives CH3–(CH2)n−2–CH2X (X = H, Br, Cl, I) Calculated within a Simple Additivity Model
10−37 esu = 1.4 × 10−51 MKSA (SI units).
The γH values are determined from alkane series and subsequently used in order to determine γX values.
Table 4
Values of α and β Parameters and Proper Volumes VX for the Studied Alkanes and Substituted Alkanes CH3–(CH2)n−2–CH2X (X = H, Cl, Br, I) Determined as Described in Text (in A3)
X
H
Cl
Br
I
α
−3.73447
−0.42269
0.95629
2.0142
β
113.9475
119.46
122.42
131.747
VX
56.974
62.482
65.446
74.773
Table 5
Dielectric Constant for an Infinite –(CH2)n−2 Chain (n → ∞) and for the –CH2X Group (∊X) Calculated for a Sodium D Line
X
∊2(–CH2)n→∞
∊X
H (alkanes)
2.17483
1.57821
Cl
2.17483
2.16237
Br
2.17483
2.52426
I
2.17483
3.02493
Table 6
Third-Order Hyperpolarizabilities of the –CH2 (γ2) and –CH2X (γX; X = H, Cl, Br, I) Groups (in 10−37 esu) Determined as Described in Text
Coherence Length, Refractive-Index Dispersion, and Cubic Susceptibilities for Studied Alkanes and Substituted Alkanes at 1.064 μm and at Room Temperature (20°C)a
The precision in coherence-length determination is better than 1% and the relative precision in χ(3) better than 2%.
10−14 esu = 1.4 × 10−22 MKSA (SI units).
Table 3
Group Hyperpolarizabilities (in 10−37 esu)a for Studied Alkanes and Alkane Derivatives CH3–(CH2)n−2–CH2X (X = H, Br, Cl, I) Calculated within a Simple Additivity Model
10−37 esu = 1.4 × 10−51 MKSA (SI units).
The γH values are determined from alkane series and subsequently used in order to determine γX values.
Table 4
Values of α and β Parameters and Proper Volumes VX for the Studied Alkanes and Substituted Alkanes CH3–(CH2)n−2–CH2X (X = H, Cl, Br, I) Determined as Described in Text (in A3)
X
H
Cl
Br
I
α
−3.73447
−0.42269
0.95629
2.0142
β
113.9475
119.46
122.42
131.747
VX
56.974
62.482
65.446
74.773
Table 5
Dielectric Constant for an Infinite –(CH2)n−2 Chain (n → ∞) and for the –CH2X Group (∊X) Calculated for a Sodium D Line
X
∊2(–CH2)n→∞
∊X
H (alkanes)
2.17483
1.57821
Cl
2.17483
2.16237
Br
2.17483
2.52426
I
2.17483
3.02493
Table 6
Third-Order Hyperpolarizabilities of the –CH2 (γ2) and –CH2X (γX; X = H, Cl, Br, I) Groups (in 10−37 esu) Determined as Described in Text
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