Материал: Weber H., Herziger G., Poprawe R. (eds.) Laser Fundamentals. Part 1 (Springer 2005)(263s) PEo

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224

4.3.3 Individual scattering processes

[Ref. p. 232

g(ωS) =

gS Γ 2

(4.3.13)

.

(ωS − ωL + ωo)2 + Γ 2

A Lorentzian lineshape is assumed in (4.3.13) that holds well in gases at su ciently high pressure, weakly associated liquids and solids. SRS of notably depolarized Raman lines is discussed in [78Lau]. Frequency shifts observed for SRS in the generator setup are compiled in Table 4.3.1. A list of gain factors gS and other parameters is presented in Table 4.3.2. The relaxation time T2 in condensed matter is in the range 10−12 to 10−10 s.

Table 4.3.1. Frequency shifts (in wavenumber units) observed in stimulated Raman scattering of various materials.

(a) Liquids

Medium

Stokes shift

Excitation

Reference

ν0/c [cm−1]

wavelength [nm]

Acetic acid

2944

[84Kru]

Acetone

2925

527

[68Bre, 69Col]

Aniline

997

694

[66Eck]

Benzaldehyde

1001

694

[66Bar]

Benzene

992

527

[67Sha, 68Bre, 69Col, 70Alf]

Benzene

3064

694

[66Eck]

Benzene-d6

944

694

[67Blo]

Benzonitrile

2229

694

[66Eck]

Bromobenzene

998, 1000

527, 694

[66Eck, 67Sha]

Bromopropane

2962

694

[66Bar]

2-Bromopropane

2920

694

[66Bar]

1-Bromopropane

2935

694

[66Bar]

Butyl-benzene (tert.)

1000

694

[66Bar]

Carbondisulfide

656

527

[67Sha, 68Bre, 69Col, 70Alf]

Carbontetrachloride

460

694

[66Eck]

Chlorobenzene

1002

527

[67Sha, 69Col]

Chloromethylbutane

2927

694

[66Bar]

Chloroform

663

694

[66Eck]

Cyclohexane

2825

[84Kru]

Cyclohexanone

2683

694

[66Eck]

1,3-Dibromobenzene

992

694

[66Bar]

1,2-Dichloroethane

2958

[84Kru]

Dichloromethane

2989

[75Lau]

2,2-Dichlorodiethylether

2938

527

[83Tel]

1,2-Diethylbenzene

2934

694

[66Bar]

1,2-Dimethylcyclohexane

2853, 2921

694

[66Bar]

1,4-Dimethylcyclohexane

2876

694

[66Bar]

Dimethylhexadiene

2910

694

[66Bar]

1,4-Dioxane

2967

[84Kru]

DMSO, dimethylsulfoxide

2911

[95Go]

Ethanol

2928

527

[69Col, 71Lin]

Ethyl-Benzene

1002

694

[66Eck]

1-Fluoro-2-chlorobenzene

1034

694

[66Bar]

Fluorobenzene

1009

694

[66Eck]

Fluoromethane

2970

694

[78Map]

Isopropanol

2882

527

[69Col]

Methanol

2835

527

[69Col, 70Alf]

Methanol-d4

2200

527

[73Lau]

3-Methylbutadiene

1638

694

[66Eck]

(continued)

Landolt-B¨ornstein

New Series VIII/1A1

Ref. p. 232]

4.3 Stimulated scattering

225

Table 4.3.1a continued.

Medium

Stokes shift

Excitation

Reference

ν0/c [cm−1]

wavelength [nm]

Nitrobenzene

1344

527, 694

[67Blo, 67Sha, 69Col]

2-Nitropropane

2945

694

[66Bar]

Nitrogen (T = 77 K)

2326

527

[74Lau]

1,3-Pentadiene

1655

694

[66Eck]

Piperidine

2933

694

[66Eck]

Pyridine

992

694

[66Eck]

Siliciumtetrachloride

425

527

[71Lau]

Styrene

1315, 1631, 3056

694

[66Eck]

Tintetrabromide

221

527

[78Lau]

Tintetrachloride

368

527

[78Lau]

Tetrachloroethane

2984

694

[66Eck]

Tetrachloroethylene

448, 2939

527

[69Col, 72Lau, 66Bar]

Tetrahydrofuran

2849

694

[66Eck]

Toluene

1004

527, 694

[67Blo, 67Sha]

Water

3450

527

[68Bre, 69Col, 69Rah]

m-Xylene

2933

694

[66Eck]

o-Xylene

2913

694

[66Eck]

p-Xylene

2998

694

[66Eck]

(b) Solids

Medium

Stokes shift

Excitation

Reference

ν0/c [cm−1]

wavelength [nm]

Al2O3

416

532

[97Kam2]

1-Bromonaphthalene

1363

694

[66Eck]

Calcite

1086

527

[69Col]

1-Chloronaphthalene

1368

694

[66Eck]

Diamond

1332

527

[71Lau]

2-Ethylnaphthalene

1382

694

[66Bar]

Gd2(MoO4)3

960

532

[97Kam1]

LiHCOO · H20

104, 1372

694

[90Lai]

NaClO3

936

532

[97Kam3]

Naphthalene

1380

694

[66Eck]

Polydiacetylene

1200

[94Yos]

Sulfur

216, 470

694

[66Eck]

(c) Gases

Medium

Stokes shift

Excitation

Reference

ν0/c [cm−1]

wavelength [nm]

Ammonia

3339

[72Car]

Barium vapor

11395

552

[83Sap, 87Glo]

Ethylene (55 atm)

1344

694

[70Mac]

Butane (90 atm)

2920

694

[70Mac]

Carbondioxide (20–50 atm)

1385

694

[70Mac, 78Map]

Carbonmonoxide

2145

694

[72Car]

(continued)

Landolt-B¨ornstein

New Series VIII/1A1

226

4.3.3 Individual scattering processes

[Ref. p. 232

Table 4.3.1c continued.

Medium

Stokes shift

Excitation

Reference

ν0/c [cm−1]

wavelength [nm]

Cesium vapor

14597

[84Har]

Chlorine

556

694

[72Car, 78Map]

Deuterium

2991

694

[67Blo]

Hydrogen

4160

694

[67Blo, 75Cha]

Hydrogenbromide (20 atm)

2558

694

[70Mac, 78Map]

Hydrogenchloride (35 atm)

2883

694

[70Mac, 78Map]

Methane (10 atm)

2917

[70Mac]

Nitrogen (55–100 atm)

2330

694

[70Mac, 75Cha]

N2O (50 atm)

774

694

[70Mac, 78Map]

NO

1877

694

[72Car]

Oxygen (50–100 atm)

1550

694

[70Mac]

SF6 (15–20 atm )

1551

694

[70Mac]

SF6 (18 atm)

775

694

[72Car]

Table 4.3.2. Gain factor and other parameters of stimulated Raman scattering.

(a) Liquids

Medium

Stokes shift

Scattering

Linewidth

Gain factor

Excitation

Ref.

ν0/c

coe cient

δν/c

gS

wavelength

[cm−1]

N × dσ/dΩ

[cm−1]

[1012 m/W]

[nm]

[107 m−1 sr−1]

Acetone

2925

17.4

12

530

[69Col]

Benzene

992

2.2

28

694

[72Mai]

Bromobenzene

1000

15

1.9

15

694

[72Mai]

Carbondisulfide

655

75

0.50

240

694

[72Mai]

Chlorobenzene

1002

15

1.6

19

694

[72Mai]

Ethanol

2928

17.4

51

530

[69Col]

Isopropanol

2882

26.7

9.2

530

[69Col]

Methanol

2834

18.7

23

530

[69Col]

Methanol

2944

26.5

18

530

[69Col]

Nitrogen

2326

2.9

0.067

170

694

[72Mai]

Nitrobenzene

1345

64

6.6

21

694

[72Mai]

Oxygen

1552

4.8

0.117

140

694

[72Mai]

Tetrachloroethylene

447

17

598

[76Mai]

Toluene

1003

11

1.9

12

694

[72Mai]

1,1,1-Trichloroethane

2939

5.2

51

530

[69Col]

Water

3450

430

1.4

530

[69Col]

Landolt-B¨ornstein

New Series VIII/1A1

Ref. p. 232]

4.3 Stimulated scattering

227

(b) Solids

Medium

Stokes shift

Linewidth

Gain factor

Excitation

Ref.

ν0/c

δν/c

gS

wavelength

[cm−1]

[cm−1]

[1012 m/W]

[nm]

Ba2NaNb5O15

650

67

694

[72Mai]

Calcite

1086

1.1

1.4

530

[69Col]

CuAlS2

314

21,000

514

[97Bai]

GaP

403

19,000

632

[97Bai]

6LiNbO3

256

180

694

[72Mai]

7LiNbO3

256

89

694

[72Mai]

6LiTaO3

600

43

694

[72Mai]

Quartz

467

0.15

527

[67Wig]

(c) Gases

Medium

Stokes shift

Di erential

Dephasing

Gain factor

Excitation

Ref.

ν0/c

scattering

time T2

gS

wavelength

[cm−1]

cross section

[ps]

[1012 m/W]

[nm]

dσ/dΩ

[1036 m2 sr−1]

H2, Q(1)

4155

1.2

208

9.7

1064

[86Han]

H2, Q(1)

4155

79

208

27.6

532

[86Han]

D2, Q(2)

2987

2.0

150

3.7

1064

[86Han]

D2, Q(2)

2987

8.0

150

10

532

[86Han]

Methane, Q

2917

7.0

16

3.3

1064

[86Han]

Methane, Q

2917

270

16

8.6

532

[86Han]

4.3.3.2Stimulated Brillouin scattering (SBS) and stimulated thermal Brillouin scattering (STBS)

Stimulated Brillouin scattering was extensively studied in liquids, solids, and gases. In many substances it is the dominant process under stationary conditions and occurs generally in backward direction. The scattering originates from two coupling mechanisms between the electromagnetic field and the medium: electrostriction and absorption. In transparent media only electrostriction is relevant. In absorbing media the second contribution called Stimulated Thermal Brillouin Scattering (STBS) is caused by absorption-induced local temperature changes leading to propagating density waves. The frequency dependencies of the gain factors for the two mechanisms are di erent. The peak values of stimulated gain are given by:

ge

(∂ε/∂ρ)2

ω2 ρo

=

T

S

(4.3.14)

B

2 c3 nS v ΓB

for the electrostrictive contribution (superscript “e”), and by

ga

=

α (∂ε/∂ρ)T ωS βT

(4.3.15)

B

4 c nS Cp ΓB

for STBS. Here (∂ε/∂ρ)T is the change of the relative dielectric constant with mass density ρ at constant temperature T . ρo is the equilibrium density value. v denotes the sound velocity at

Landolt-B¨ornstein

New Series VIII/1A1

228

4.3.3 Individual scattering processes

[Ref. p. 232

frequency ωo = ωL − ωS (see (4.3.4) for backward scattering, θ = 180◦ ). The parameters in (4.3.15) are the absorption coe cient of the laser intensity α and the relative volume expansion coe cient βT . The half-width ΓB = π δν of the corresponding spontaneous Brillouin line that displays an approximately quadratic frequency dependence also enters the expressions above. For liquids one can write:

4

η S + Λ

1

1

+ η V

=

−

,

ΓB

3

CV

Cp

(4.3.16)

ωo2

2 ρo v2

where η S and η V, respectively, denote the shear and volume viscosity; the latter is to some extent frequency-dependent via relaxation phenomena. Λ is the thermal conductivity. CV and Cp are

the specific heat per unit mass at constant volume and pressure, respectively. The phonon lifetime τ of the involved acoustic phonons with circular frequency ωo is related to the linewidth by τ = T2/2 = 1/(2 ΓB) . The peak gain value gBa increases proportional to α and is of same order of magnitude as gBe for α ≈ 1 cm−1 .

The total frequency-dependent gain factor for the (first-order) Stokes component of SBS in-

cluding STBS is given by

g(ω

) =

gBe ΓB2

gBa 2 ΓB (ωS − ωL + ωo)

.

(4.3.17)

(ωS − ωL + ωo)2 + ΓB2 −

S

(ωS − ωL + ωo)2 + ΓB2

The maximum contribution of STBS is red-shifted relative to the Brillouin line and occurs at ωS = ωL −ωo −ΓB . In the blue wing of the Brillouin Stokes line the mechanism produces stimulated loss. Equation (4.3.17) states that the Stokes shift observed in the stimulated Brillouin scattering of absorbing media in the generator or oscillator setup – occurring at the peak value of g(ωS) – is modified compared to the spontaneous Brillouin line.

A list of frequency shifts observed in SBS of transparent media is presented in Table 4.3.3 where values for the Brillouin linewidth δν and the gain parameters gBa /α and gBe are also compiled. The relaxation time T2 (= 1/π δν) in condensed matter is in the order of 10−9 s so that SBS is close to steady state for giant laser pulses with tp ≈ 10−8 s (if self-focusing is avoided), but is of transient character in the subnanosecond time domain.

4.3.3.3Stimulated Rayleigh scattering processes, SRLS, STRS, and SRWS

Three mechanisms can be distinguished:

1.Stimulated Rayleigh Line Scattering in transparent substances, SRLS, by electrostrictive coupling to non-propagating density changes,

2.Stimulated Thermal Rayleigh Scattering, STRS, by absorptive coupling similar to the STBS case, and

3.Stimulated Rayleigh Wing Scattering, SRWS, in liquids by orientational changes of anisotropic molecules.

The frequency shifts of the Stokes component of the first two cases are considerably smaller than for SBS. SRLS is di cult to observe because of the small gain factor and the relatively long relaxation time T2 ≈ 10−8 s for backward scattering leading to transient scattering for nanosecond pulses.

Landolt-B¨ornstein

New Series VIII/1A1

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