Appl. Phys.

11,209--231(1976)
Applied
Physics
9 by Springer-Verlag 1976

Applications of Stimulated Raman Scattering

M a x Maier
Fachbereich Physik, Universit~it Regensburg, D-8400 Regensburg, Fed. Rep. Germany

Received20 April 1976/Accepted5 July 1976

Abstract. The applications of stimulated Raman scattering reviewed in this paper include:
determination of spontaneous Raman parameters and nonlinear susceptibilities by gain
measurements and coherent anti-Stokes Raman spectroscopy, excitation of molecular
vibrations and lattice waves and measurement of their relaxation times, generation of
intense tunable light in the infrared region of the spectrum. The main results of the theory
of stimulated Raman scattering relevant to the understanding of these applications are
discussed.

PACS Codes:78.30, 32

Since the discovery of stimulated Raman scattering
in 1961 extensive literature has accumulated on various
aspects of this phenomenon. The results of these
investigations have been discussed in several review
articles [1-6]. In this paper, important applications
of stimulated Raman scattering which have been sub-
ject of intense research in recent years are reviewed.
The main emphasis is put on Raman scattering from
molecular vibrations and lattice waves, while spin-flip
Raman scattering in solids and electronic Raman
scattering from atoms in gases are discussed only
shortly.
Spontaneous Raman scattering has been well known
for approximately fifty years. A small portion of the
incident light is scattered in all directions.The frequency
of the scattered light is shifted by the frequencies of
the molecular vibrations or phonons to shorter or
longer wavelengths corresponding to the anti-Stokes
and Stokes lines, respectively. Quantitative measure-
ments of the spontaneous Raman spectrum allow the
determination of the frequency shifts, linewidths and
scattering cross sections of the Raman lines.
When the intensity of the light beams incident onto
the Raman medium is increased by using powerful
lasers stimulated Raman scattering occurs. Stimulated
Raman scattering differs from the spontaneous phe-
nomenon by the high intensity, the small divergence,
and the narrow linewidth of the scattered light. These
properties of stimulated Raman scattering can be
explained mainly by the high exponential amplifica-
tion of the spontaneously scattered light by a factor
up to 1013. Usually only the Raman line with the largest
gain is observed experimentally. The generation of
stimulated Raman scattering is accompanied by intense
molecular or lattice vibrations which have a high
degree of temporal and spatial coherence. These
molecular vibrations modulate the incoming light
beam and generate side bands. In this way, higher-
order Stokes and anti-Stokes lines are emitted which
have all the same frequency separation. The anti-
Stokes emission and part of the Stokes emission is
observed in cones with angles of typically several de-
grees.
Three different experimental situations are distin-
guished in stimulated Raman scattering (see Fig. 1).
a) Generator system: The laser light is incident to the
Raman medium and amplifies the spontaneously
scattered light to high intensity during one pass through
the medium.
b) Oscillator system: The Raman medium is enclosed
in a resonator with highly reflecting mirrors.
c) Amplifier system: In this travelling wave system
both laser (pump) light and Raman (signal) light are
210 M. Maier
@ RAMANGENERATOR
coL
@ RAMAN OSCILLATOR
M RM M a detailed discussion of the generation of ultrashort
9 coL
@ R A M A N AMPLIFIER
Fig. 1. (a) Raman generator; (b) Raman oscillator; (c) Raman ampli-
fier. (RM: Raman active medium, M: mirror; ~OL,COS,C0A:frequencies
of laser, Stokes, and anti-Stokes light, respectively)
incident to the Raman medium. The signal light is
amplified at the expense of the pump light.
The applications of stimulated Raman scattering which
will be discussed in this paper are presented in Fig. 2.
The figure shows schematically the experimental
methods, the results, and the measured parameters.
For an explanation of details the corresponding sec-
tions should be consulted. In Figs. 2a and b the determi-
nation of Raman spectra by gain measurements (Sub-
sec. 2.1) and coherent anti-Stokes Raman scattering
(CARS) (Subsec. 2.2) are shown, respectively. From
these experiments spontaneous Raman data and values
of the third-order nonlinear electronic susceptibilities
are obtained. They have also been used to determine
the concentration of components of mixtures and the
temperatures of gases. Information on Raman spectra
has also been obtained by inverse Raman scattering,
i.e. by measuring induced absorption at anti-Stokes
frequencies [7-14]. Figure 2c presents an important
application of the excitation of molecular vibrations
by stimulated Raman scattering. Relaxation times of
molecular and lattice vibrations have been determined
using Raman scattering of light (Subsec. 2.3). The
excitation of molecular vibrations by SRS has also
been used in chemical reactions [15] and in the
measurement of the polarizability of higher vibrational
states of molecules [16, 17]. It has been suggested,
recently, to use the stimulated Raman process in
photoselective isotope enrichment [ 18"].The generation
of intense tunable infrared radiation by SRS with
tunable lasers (Subsec. 2.4.1) and by stimulated po-
lariton scattering (Subsec. 2.4.2) is shown in Fig. 2d. It
should be noted that tunable infrared light can also be
generated by parametric Raman processes and by
stimulated spin-flip Raman scattering. In addition, SRS
has been used to extend the spectrum of intense lasers
into the ultraviolet wavelength region [19, 20]. For
pulses by SRS the reader is referred to [2].
1. Theory
In this section we summarize the theoretical results
which are relevant for the applications of stimulated
Raman scattering discussed in the experimental part
of the paper. For simplicity, we concentrate on Raman
scattering from molecular vibrations and lattice waves.
The theory of electronic Raman scattering from gases
and solids and of spin-flip Raman scattering in solids
is not treated here.
1.1. Wave Equation and Nonlinear Polarization
The propagation of light waves in a medium is described
by the wave equation for the electric light field E
n 2 D2E 4~z 02P Nc
A E - c2 Ot2 - c2 t~t2 (1)
pNL is the nonlinear polarization, n the refractive index,
and c the velocity of light in vacuum. We assume that
the electric field is described by plane waves with
slowly varying amplitudes and phases propagating in
the z-direction [1, 2, 21-23].
E(z, t)= 1 {EL exp [i(kLZ-- mEt)] + E s exp [i(ksz- Cbst)]
4- E A exp [i(kAZ-- O a t ) ] -t- C.C.} . (2)
k and co are the wave vector and frequency of the light
field, respectively. The indices L, S, and A stand for
the laser, Stokes, and anti-Stokes components, and
c.c. for the complex conjugate. The nonlinear polariza-
tion is written as
PNL(z,t)= 1 {pUL exp (-- iCOLt) + p~L exp (-- iCOst)
+ p~L exp (-kOAt ) + c.c.}. (3)
Neglecting second derivatives of the electric fields
with respect to space and time, e.g. O2Es/OZ2~ ksOEs/OZ,
 Applications of Stimulated Raman Scattering 211

Experimental m e t h o d E x p e r i m e n t a l results Measured parameters

a} gain m e a s u r e m e n t (Sec. 2.1) Raman s p e c t r u m (gain l i n e w i d t h 6~,

factor g versus f r e q u e n c y m) Raman scattering cross

~'~ J l> ~L ~s
g,
section do/dQ

us

b) C o h e r e n t a n t i - S t o k e s Raman spectrum m o d i f i e d by iRaman parameters ~w, d o / d Q

Raman scattering (CARS) electronic c o n t r i b u t i o n s !third-order nonlinear electronii
(Sec. 2.2) (anti-Stokes intensity IA susceptibility
versus f r e q u e n c y m)
C o n c e n t r a t i o n s in m i x t u r e s and
IA , t e m p e r a t u r e of gases

wL
w5

O) E x c i t a t i o n of m o l e c u l a r
v i b r a t i o n s by SRS (Sec. 2.3.1)
D e t e c t i o n by d e l a y e d CARS
(Sec. 2.3.2)
T e m p o r a l decay of CARS
(anti-Stokes intensity ICARS
v e r s u s d e l a y time t bet-
ween pump (LI) and ~ r o b e pulse
R e l a x a t i o n times of m o l e c u l a r
Jvibrations
D e p h a s i n g time T of m o l e c u l a r
vibrations

WL2
~ ~ , ~ I, I LI'~S1
69. (L2)

<)
't D

D e t e c t i o n by d e l a y e d incohe- T e m p o r a l decay of incoherent E n e r g y r e l a x a t i o n time T'

(Sec'2"3"~(l)A2
rent a n t i - S t o k e s scattering anti-Stokes intensity
(anti-Stokes i n t e n s i t y IA
versus d e l a y time tD)
of m o l e c u l a r v i b r a t i o n s

L1~
WL2
:-"~ ~L.1,WS1
,/---.___
- ~t D

~) S t i m u l a t e d R a m a n scattering S t i m u l a t e d Raman spectrum Tunable infrared r a d i a t i o n

w i t h tunable lasers (Sec. 2.4.1)
I,
(Intensity I v e r s u s f r e q u e n c y w)

>I I-~WS2~'-~WS2 I

(~)L g-)St (1)S2 (~$3

Stimulated polariton Infrared f r e q u e n c y W I R v e r s u s Tunable infrared r a d i a t i o n
scattering (Sec. 2.4.2) tuning angle e

WIR

" WL f 8~

Fig. 2. Applications of stimulated Raman scattering

212 M. Maier
we obtain from (1)-(3)
ns 0Es ~?Es 2nicos
+ -- - PsNz exp ( - iksz) (4)
c & & cn s
and equivalent equations for the anti-Stokes and laser
fields E a and EL, respectively.
In this paper, we are interested in the induced polariza-
tion of third order in electric field strength, which can
be expressed as
p N L ( z , t) = zE(z, t)E(z, t)E(z, t) . (5)
The third-order nonlinear susceptibility Z is, in general,
a complex fourth-rank tensor with elements Z~m,o which
depend on the frequencies COL,COS,and COA.It will be
discussed in detail below.
The l-th Cartesian component of the nonlinear polari-
zation at the Stokes frequency is given by
p~L = 3 Z (Z,,,,o(- COs,COL,oL, - O,)A)ELmELnE~o
m , tl, o
9exp [i(2k L- kA)Z]
+ 2ZZm,o( -- COS,COL, -- COL,COs)ELmE*,Eso exp (iksz)}.
(6)
Here, the convention of Maker and Terhune [23] has
been used, i.e. a factor 1/4 has been included in the
nonlinear susceptibility )~. Since the ordering of the
electric fields is unimportant, the last three frequencies
in Z may be interchanged at will provided that the
coordinate indices are interchanged in the same man-
ner. It will be shown in the following sections that -
the first term in the brackets of(6) leads to a parametric
generation of Stokes light (see Subsec. 1.3.2), while the
second term corresponds to an exponential amplifica-
tion (see Subsec. 1.3.1). Similar equations are obtained
for the polarization at the laser and anti-Stokes
frequencies.
1.2. Third-order N o n l i n e a r Susceptibility
1.2.1. Spatial Symmetry [22]
The number of non-vanishing components of the non-
linear susceptibility tensor depends on the symmetry
of the material. In a medium of cubic symmetry there
are, in general, four independent tensor components
Z . . . . . Zxxyy, )~xyyx, and Zxyxy, where the x- and y-direc-
tions are chosen parallel to the cubic axes and the light
beams propagate in the z-direction. In isotropic mate-
rials, e.g. liquids, the number of components is reduced
to three by the isotropy condition
Z. . . . = Z~yy + Z~yy~+ Zxyxy. (7)
There is an additional condition for the nonlinear
susceptibility responsible for parametric anti-Stokes
(or Stokes) generation, which follows by interchanging
the second and third coordinate indices and the
corresponding frequencies in the brackets
Zxxyy( -- (DA' COL' COL' - - ('OS) ~-- )~xyxy( - - (D A' COL' COL' - - COS)"
(8)
1.2.2. Frequency Dependence [23 25]
There are three different contributions to the nonlinear
susceptibility: from non-resonant electronic processes,
from two-photon absorption, and from stimulated
Raman-scattering processes [23, 24]. The processes
are schematically shown in Fig. 3 for the case of
coherent anti-Stokes Raman scattering.
i) The nonresonant electronic contributions 7ff due
to virtual transitions are depicted in Figs. 3a and b.
When the material is transparent at the laser, Stokes,
and anti-Stokes frequencies there is only a slight
variation of Znr with frequency. In addition, )~nr is a
real quantity.
ii) When 2coL is resonant with two electronic levels
of the same parity, two-photon absorption occurs
(see Fig. 3c). The contribution )(v of two-photon ab-
sorption processes to the nonlinear susceptibility is
complex and may be combined with the non-resonant
contribution to yield the total complex electronic
susceptibility
e nr tp
)~lmno = Zlm.o ~- )~lmno " (9)
@ @ @ @
-~-- - j ~
h ~ h~ L ~~
non resonant two photon Raman
processes absorption resononce
resononce
Fig. 3a d. Contributions to the third-order nonlinear susceptibility.
(a) and (b) non-resonant electronic contributions, (c) two-photon
absorption resonance, (d) R a m a n resonance. Dashed lines denote
virtual levels whereas the solid lines stand for real energy states [24]
 Applications of StimulatedRaman Scattering 213

iii) In this paper we are mainly concerned with the For a solution of (10) we assume that the molecular
contribution ZR of Raman-active vibrational modes vibrations are driven near resonance by the laser and
to the third-order susceptibility (see Fig. 3d). An ex- Stokes fields, EL and Es respectively, and write
pression for the Raman contribution will be derived
in the following section for the case of one Raman- 1
q~v= ~ {q exp [i(kL-- ks)z- i(coL- COs)t]+ c.c.}. (13)
active vibration with resonant frequency coo and
damping constant F in the frequency region of interest.
The total third-order susceptibility is the sum of the We insert (2) and (13) into (10) and make the following
electronic and Raman contributions. approximations: We neglect the anti-Stokes field EA
in (2) and the second derivative of the amplitude q of
the molecular vibrations with respect to time; on the
1.2.3. Raman Susceptibility right hand side of (14) we include only the term
The Raman contribution to the nonlinear susceptibility driving the vibration in resonance, i.e.
is derived from the differential equations describing
the Raman-active vibrations. We assume that the c?q i t?c~
& iq(COL-- COS--COo+ iF~2) = ~4(o0 0q ELE* A. (14)
vibrational energy levels of the molecules we are
interested in can be represented by a two-level system
consisting of ground and first excited state. This The Raman contribution to the nonlinear polariza-
assumption is fulfilled when the molecular vibration tion is given by
is sufficiently anharmonic. The following differential
equations for the expectation value qa, of the displace- P =Nqav~qE. (15)
ment operator q of the molecular vibration and the
difference A in probability of finding the molecule
in the ground and excited state are obtained [26, 27]. N is the number of molecules per unit volume. When
the vibrations are heavily damped, (14) is easily solved
c~2q. . . . 0q~ +~o2G~ = 1 0~ by neglecting Oq/&. In this case, we calculate the non-
~t 2 -h l - ~ - 2m c~qE2 A , (10)
linear polarization at the Stokes frequency
c3A 1 g~ E2 0q~
& -- hcoo 0q ~- +r'(1-A). (11) p i L- NA 1
8coom coo - (coL- COs)+ iF/2
,Here m is the reduced mass associated with the vibra- [&/ (&l*
tion. O~/Oq is the derivative of the polarizability tensor 2
m,n,o
\~q],~\~q/no ELmE*"Es~ exp (iksz) . (16)
with respect to the normal coordinate q and is related
to the RamZa matrix element ~R by Introducing the Raman matrix element (12) and com-
paring with the second term in (6) we get the Raman
( h 11/2(~1 susceptibility
c~= \2~s \~qqh,~ " (12)
R CO COS)= N J R R ,
When the local field correction is taken into account, Zlmno(-- S, COL,-- COL, 24h COo -- (COL--COS)+ iF~2"
a factor (n2+ 1)2/9 is included on the right-hand side (17)
of (12) [24].
The damping constant F corresponds to 1M, the inverse The Raman contribution Z~,,o(-cos, COL,COL,--C0A) to
phase relaxation time of the vibration, F' to 1/-c', the the first term in (6) can be calculated in a similar
inverse lifetime of the first vibrational energy level. way.
In this section we assume that the ground state For liquids and gases the susceptibility is averaged
population is not changed by the light fields, i.e. A over all orientations of the molecules. We use the
can be treated as a constant. relation between the Raman matrix element C~x~Rand
When A is taken to be constant, (10) is the equation the integrated spontaneous Raman scattering cross
of motion of a harmonic oscillator and can also be section (da/df2)x ~
used to describe the Raman-active lattice vibrations
in a crystal. (I 0(xgx[2 ) = (c/COs) 4(da/dQ)xx (18)
214 M. Maier
i i I I
laser field. In the steady state case the Stokes intensity is

/
1.0
>- amplified exponentially with the laser intensity I L and
the length l of the medium
O5
F- I a = I e exp (giLl) , for Ia~ IL. (20)
(i.
LU
ocO 0 I e and I, are the initial and amplified Stokes intensity,
Z3
c~
respectively. The Raman gain factor is given by

<~ -0.5 192n2CO~ (i)

5"
I I I I
er" -2 -1 1 2
[Oao-(cOL-
~OS)]/V
Fig. 4. Real part Za(') and negative imaginary part -Z R(~)of the
Raman susceptibility versus normalized frequency difference
[COo-(o~L-COs)]/V
and get for symmetric Raman tensors
R
( x . . . . ( - COs,COL, - coL, cos))
NA(c) 4 (da/dF2)x~
- 24h ~ss C0o--(COL--COs)+iF/2" (19)
(d6/d(2)~ is connected to the total Raman scattering
cross section (da/dg2)t via the depolarization ratio
by (da/d(2)~ = (da/d(2),/(1 + 0).
The normalized real and imaginary part of the
Raman susceptibility ZR(r) and XR(i), respectively, are
plotted versus normalized frequency difference
[COO - - (COL - - C O s ) ] / F in Fig. 4. ,~R(1) has a Lorentzian
frequency dependence. Note that Xa(r) is positive for
COo- (COL--COs)> 0 and negative for COo- (COL--COS)< 0.
The Raman susceptibilities at the anti-Stokes frequency
can be calculated similarly to (19).
1.3. Special Solutions of the Differential Equations
In this section, we discuss several special solutions of
the material Eqs. (10) and (11) for the molecular
vibrations and the wave Eq. (1) for the light field. The
solutions are important for the discussion of the
applications of stimulated Raman scattering.
1.3.1. Raman Gain Factor [21, 22]
In calculating the steady state Raman gain factor g
we neglect the anti-Stokes component and introduce
the nonlinear polarization (6) into Eq. (4) for the
Stokes field. For simplicity, we assume that the laser
and Stokes fields are linearly polarized in the x-direc-
tion and that the Stokes field is small compared to the
g= c~n2 XXXXX(--COS'COL' - - C O L ' COS)' (21)
where )(j)~= is the imaginary part of the nonlinear
susceptibility. In a transparent medium without a two-
photon resonance the electronic contribution to the
nonlinear susceptibility is real. The imaginary part is
completely due to the Raman susceptibility (17) or (19).
Combining (19) and (21), we get
16n2c2NA(da) I"2/4
g= hCO~nZF ~ ~ [CO0_(COL_cos)]Z+F2/4. (22)
It should be noted that the gain factor has the same
Lorentzian frequency dependence with linewidth F as
the imaginary part of the Raman susceptibility (see
Fig. 4). In general, the gain factor has the same shape
as the corresponding spontaneous Raman line. T h e
spontaneous Raman linewidth and the scattering cross
section da/dO can be determined from measurements
of the Raman gain factor, see (22). When several
vibrations are Raman-active in the molecule, a sum
over the corresponding contributions has to be in-
cluded in (22).
1.3.2. Coherent Anti-Stokes Raman Scattering (CARS)
[23-253
When light at the pump and signal frequencies col
and COs,is sent into a Raman-active medium, coherent
molecular vibrations are strongly excited. The laser
beam is scattered coherently from the vibrations
generating intense anti-Stokes light. When the differ-
ence between COl and COsis far from Raman resonances
the nonlinear electronic susceptibility is responsible
for the generation of a polarization at the anti-Stokes
frequency. Again we assume that the light beams are
linearly polarized in the x-direction. The nonlinear
polarization enters the wave equation for the anti-
Stokes field E A. We get
dE~ _ 6nicoa Zxxxx(- COn,COL,COL,- - COs)E2LE*
dz cn
9exp [i(2kL-- ks - kh)Z]. (23)
 Applications of Stimulated Raman Scattering 215

C6H6
kL kL 100
Fig. 5. Phase-matching diagram for the generation of anti-Stokes light.
(OA: emission angle of anti-Stokes light; kL, ks, kA: wave vectors of
laser, Stokes, and anti-Stokes light, respectively)
10
>-
I--
For light beams traveling in the same direction phase- c0
Z
matching is not possible in transparent, isotropic media LLI

#
I--
because of the colour dispersion. When the theory is Z
extended to include arbitrary directions of the light
n
beams the phase-matching condition LI.I
N
2k L - k s - k A = 0 (24)
IE
n-
is readily fulfilled by choosing the correct angle be- O
Z
tween the incident signal and pump beam (see Fig. 5).
The anti-Stokes beam is emitted under an angle {9 g
to the propagation direction of the laser light. .01
In deriving (23) we assumed small Raman gain giLl ~ 1,
i.e. the anti-Stokes light is not attenuated and the
Stokes light is not amplified exponentially by stimu- I I I I I I I I
lated Raman scattering. For small anti-Stokes fields 980 1000 1020 10/.0 1060
E A S E L , E s and phase-matching, we obtain the anti-
Stokes intensity by integrating (23) (wL-C0S V2~c [cm -11
Fig. 6. Measured normalized anti-Stokes intensity vs frequency
I A oC JX. . . . ( - - O)A, coL, coL, - - coS)] 2 1 2 1 2 I s 9 (25)
difference (mE - COs)/2~c in benzene. Note logarithmic intensity scale
I A increases linearly with the Stokes intensity I s and [42]
quadratically with the laser intensity I2L. It is important
to note that the anti-Stokes intensity is proportional
occurs at coL - cos = coo and the minimum at COL--C~
to the absolute square of the nonlinear susceptibility. R 2 e(r)
coo + NA [~xxl /12hZx~x~- If the Raman matrix element
This leads to pronounced interference effects between
is known from measurements of the spontaneous
the different terms contributing to the susceptibility
Raman scattering cross section, see (18), a measurement
(see Subsec. 1.2.2).
of the difference 6 of the maximum and minimum
In a transparent medium with no two-photon absorp-
frequencies allows the determination of the electronic
tion when the difference frequency coL- - COSapproaches
nonlinear susceptibility
the resonance of a Raman-active vibration COo, the
(~ R 2
nonlinear susceptibility is the sum of a real non- = NAlc~xx] /12hz e(r)
.... . (26)
resonant part due to electronic nonlinearities (9) and
On the other hand, the Raman matrix element is
a complex resonant Raman susceptibility (17) or (19).
obtained from (26) when the electronic nonlinear sus-
As the difference frequency coL--cos is varied, the anti-
ceptibility is known from other experiments.
Stokes intensity goes through a maximum and a
minimum (note the logarithmic scale in Fig. 6). The
reason for the minimum is the cancellation of the 2. Experiments
positive electronic contribution by the real part of the
Raman susceptibility which is negative on the high 2.1. Raman Gain Factor
frequency side of the Raman resonance frequency (see It has been shown in Subsec. 1.3.1 that the Raman gain
Fig. 4). If the peak value of the Raman susceptibility factor contains information on the spontaneous Raman
NAI~12/12hF, see (17), is large compared to the real scattering cross section da/d~ and the Raman line-
part of the electronic term Z ~ the maximum intensity width, see (22). For precise measurements of the Raman
216
-- 89 FIBER
PD1
DYE LASERTI\
[ ,IO L10 ' O nI . I /
L2 POL
F2
F3 PD3
DYE LASER I
\ /.3 II1~
~__ C diaphragm, L: lens, POL: polarizer, FPI: Fabry-Perot inter-
SPECTROGRAPH FPI
gain factor 9 generator-amplifier experiments have been
employed. A weak signal beam is produced in the
generator cell and amplified in the presence of a strong
pump beam in the amplifier cell. Early experiments
(see e.g. [2]) suffered from disturbing effects, e.g. self-
focusing or stimulated Brillouin scattering, in the
generator cell [28, 29]. Only in a few substances where
stimulated Raman scattering is the dominant non-
linearity generator-amplifier experiments were carried
out [30-33].
Bloembergen et al. [30] have measured the Raman gain
of the Q(1) vibrational Stokes line in H2 gas. The signal
light I e was produced by stimulated Raman scattering
in a generator cell. It was strongly attenuated by a
Stokes absorber before entering the amplifier cell to
avoid saturation effects. By measuring the input I e
and output signal I, of the amplifier cell for different
cell lengths the authors verified the exponential de-
pendence of the output signal on the cell length l, see
(20). The measured Raman gain was approximately
constant in the density range where the Raman line-
width is pressure broadened. This result is in good
agreement with theory.
Valuable information on the spontaneous Raman line-
width in H2 gas has been obtained by Lallemand et al.
[31]. The frequency of the signal light was tuned by
changing the pressure in the generator cell. In this way
the gain factor was measured as a function of frequency
for H2 gas in the amplifier cell. According to (22) the
width of the measured gain curve is equal to the
spontaneous Raman linewidth. The Raman linewidth
was determined from the gain curves as a function
of gas density in the amplifier cell. Collisional narrow-
ing of the Q(1) vibrational Raman line of H 2 was
observed in the density range around 10 amagat for
backward Raman scattering.
M. Maier
'13
I
Fig. 7. Experimental setup for the investigation of the Raman
gain in a liquid-core fiber (PD: photodiode, F: filter, D:
ferometer, C: camera) [37]
Narrow linewidths have been determined for spin-flip
Raman scattering by gain measurements with a CO
laser [34, 35]. For n-type InSb with an electron con-
centration of 8 x 1014 cm -3 a Raman linewidth of 3 G
at 2 K was measured (corresponding to 200 MHz) [34].
Because the spin-flip linewidth is extremely narrow it
is not accessible by conventional spectroscopic tech-
niques.
Raman spectra of liquids were obtained from measure-
ments of the Raman gain as a function of frequency
using tunable dye lasers as light sources E36, 37]. In
Fig. 7 the experimental setup for amplification mea-
surements in liquid CC14 and C2C14 is shown sche-
matically. Two pulsed dye lasers with narrow emission
spectra (<0.1 cm -1) provide the pump and signal
pulses. Both light beams are combined by a beam
splitter and launched into a liquid-core fiber to reach
the high light intensities necessary for amplification.
By tuning the frequency of one of the dye lasers the
Raman gain is measured versus frequency. In Fig. 8
the measured normalized gain factor (a) of the v2-
vibration in liquid C2C14 with a frequency of 447 cm- 1
is compared with the normalized spontaneous Raman
power (b) [37]. Both spectra are in good agreement.
From the measured absolute value of the peak Raman
gain factor g = 1.7 x 10 . 9 cm/W at 2L= 597.6 nm the
spontaneous Raman scattering cross section ( & r / d f 2 ) x x
has been calculated, see (22).
An absolute value of the Raman gain factor of fused
quartz of 9=1.5 x 10 -11 cm/W at laser and Stokes
wavelengths of 526.0 and 535.5 nm, respectively, has
been measured in [38]. In the experiments a single-
mode clad fiber with a fused quartz core was used.
Measurements of the Raman gain of the 0-1 vibrational
Q branch of atmospheric N z over a path length of
8.53 m were carried out in [39] with a ruby laser of
 Applications of Stimulated Raman Scattering 217

It should be noted that the nomenclature for CARS

, ,l4 0
i i i i ,
0
(D is not uniform in the literature. The following notations
are frequently used: third-order frequency mixing,
Z three-wave mixing, four-wave mixing, four-photon
(.9 mixing, four-frequency mixing, active Raman spectros-
0.5 copy, spectroscopy in k-space. The discussion of the
N experiments on CARS is divided into two parts accord-
_A

I[
+ ing to the purpose of the measurements: determination
gZ o I
of the various components of the nonlinear suscepti-
.42 446 450 1.54 458 bility Z and practical application as a spectroscopic
(~0L-O~S)/2T~c[cm-1] tool, e.g. for monitoring temperatures and for con-
tic centration measurements.
LI.I i , l i i

~
O
13..
| 2.2.1. Measurements of the Nonlinear Susceptibility
1.0 C2C1/.
Z
Following the pioneering work of Maker and Terhune
IE
< [23] who investigated solids and liquids, the first
0.5
rr"

measurements of the nonlinear susceptibility in gases

N using CARS were carried out by Rado [40]. The mea-
...J
sured values range from Z~xx= 8.7 x 10 -2~ cm3/erg for
I[
n.- He to 6.2x 10~ 18 cm3/erg for C2H6 (see Table 1). In
o 0
Z
4/-,2 446 450 454 458
more recent measurements [41] a substantially larger
value of 3.7 x 10-19 cm3/erg was found for He.
(OJk-~S ) / 2 ~ c [crn -1]
The experimental setup for recent precise measure-
Fig. 8a and b. Raman spectrum of the v2-vibration of C2C14; (a) gain ments is shown in Fig. 9 [24 I. A nitrogen laser with
factor and (b) spontaneous scattering power normalized to the peak a peak power of 1 MW pumped two dye lasers whose
values of CC14 (458 c m - l) [37] frequencies could be varied by turning the gratings by
stepping motors. The 60 kW linearly polarized output
of each laser was split into two beams one of which
high power. When the pump and signal light are in
resonance with the molecular vibrations, i.e. Table 1. Real part of the third-order nonlinear electronic susceptibility
COL-- COS= COo,the peak value of the Raman gain factor 9 Z~)~x ( - C0A,COL,COL,-- COS)of gases at 1 atm pressure. Laser wave-
is proportional to the spontaneous Raman scattering length 2L = 694.3 rim, Stokes wavelength As= 975.6 nm
cross section da/df2, see (22). From the measured Raman
Gas ~,e(r)
Lxxxxk
( -- r,~
~ A ~ J Lr , ~~ O ) L ~ -- COS)
gain a value of the Raman scattering cross section of [10 is cm3/erg]
d(r/df2 = 1.82 x 10- 31 cm2/sr x molecule was calculated
in [39]. (a) (b)
The experiments discussed in this section show the
He 0.087 0.37
potentialities of the Raman gain measurements.
A 1.55
i) High resolution Raman spectroscopy is possible D2 1.30
where the final resolution is determined by the narrow Nz 1.35 1.35
linewidths of the pump and signal lasers. Oa 1.30 1.26
ii) Absolute values of Raman scattering cross sections CO 1.80
NO 4.20
are obtained from the gain factor. CH 4 2.95
SiF 4 2.25
C2H 6 6.2
2.2. Coherent Anti-Stokes Raman Spectroscopy (CARS) SF 6 2.50
Coherent anti-Stokes Raman scattering is a special CO2 2.00
case of four-wave mixing processes where the difference air 1.30
between the pump and signal frequencies coL - cos is (a) W.G.Rado: Appl. Phys. Lett. 11, 123 (1967).
close to the frequency of a Raman-active molecular (b) F.DeMartini, F.Simoni, E.Santamato: Opt. Comm. 9, 176
vibration. (1973).
218 M. Maier

LOB CAR
IB,NP5A, I
/

1 -
STEPPING I'~=[-b.I"(P_NCESAIvlpI,E
Iv~TOR DYE LASER 2 ,~ . . . . . j

"~ -- ~ -DELAYUNE I .: DOUBLE

--- |i 4ONOCHRO-
I" MATOR
N2 ., | T

~,SER .t
i| DOUBLE
_ il. o.oc..o-
[ ~,~,~,, vr,, ~ DELAY "1 " - MATOR
+
POLARIZER
-- FILTER
<lzz-~-_--z_ 4~-,__n..... . j ^ T, WHEEL
DYE LASER1 "~;z-"~':;',I'-A--V ......... " [ , - ~ - - ~ " ; , V c .LECTION Fig. 9. Experimental equipment employedin CARS
N1 I I-~EUN~IN'o SAMPLE S~'T " OPTICS
--.---1 [24]

was focused into the sample and the other into a by fitting the experimental results to theoretical curves
reference substance, e.g. a NaC1 crystal. The angle be- of the form (25) including all contributions to the non-
tween the two beams in the sample was chosen to linear susceptibility (see Subsec. 1.2.2). For chloro-
fulfil the phase-matching condition (24). The anti- benzene it was necessary to include interference effects
Stokes beam was selected by a vertical slit and directed between several Raman lines to get agreement be-
into a double monochromator to eliminate light at tween theory and experiment, see also [43]. The re-
other frequencies. The signals were measured by photo- sults of the investigations are presented in Table 2 for
multipliers PMT and further processed electroni- various liquids. It should be noted that decreasing the
cally. wavelength of the laser light from 555 nm to 495 nm
Using the experimental setup of Fig. 9, Levenson and clearly increases the electronic susceptibility. This
Bloembergen [42] measured the coherent anti-Stokes dispersion effect is expected since there are strong
emission in various liquids. To scan over a Raman absorption bands in these liquids in the near ultra-
resonance the gratings in each dye laser were rotated violet spectral region.
by driving motors. The measured anti-Stokes intensity Starting with the work of Maker and Terhune [23],
for liquid benzene is shown in Fig. 6 as a function of and Yajima [44] there have been a large number of
difference frequency C~L--COs. As discussed in Sub- investigations of CARS in solids. Most of the experi-
sec. 1.3.2 the reason for the minimum in the anti-Stokes ments were carried out in centrosymmetric crystals
intensity is the cancellation of the real part of the since in these crystals the second-order susceptibility
electronic contribution (9) to the nonlinear suscepti- is forbidden by symmetry. Only contributions from
bility by the real part of the Raman susceptibility (17) the third-order susceptibility are expected. Investiga-
or (19). The difference 5 between the minimum and tions in non-centrosymmetric crystals, e.g. LiNbO3,
maximum frequencies was determined from figures GaAs, and CuC1, are complicated by the interference
similarly to Fig. 6 and used to calculate the electronic of second- and third-order contributions to the non-
contribution I~,e(r)
~xxxX
to the nonlinear susceptibility ac- linear susceptibility [45-47]. Contributions of conduc-
cording to (26). This can be done since the values of tion electrons to the nonlinear susceptibility have been
the Raman matrix elements c~R in liquids are known found in several semiconductor crystals using C O / o r
from measurements of the spontaneous Raman cross CO lasers as light sources [34, 48-50].
section da/d#2, see (18). It should be emphasized, how- Bloembergen and coworkers [24, 51-53] have carried
ever, that due to the limited accuracy of these Raman out systematic measurements of the third-order non-
measurements the accuracy of the absolute values of Z linear susceptibility in centrosymmetric crystals. The
in Tables 1 to 3 is not very high. More complete in- investigations of CARS were done with the experi-
formation on the nonlinear susceptibility is obtained mental setup shown in Fig. 9. In the experiments on
 Applications of Stimulated Raman Scattering 219

Table 2. Third-order nonlinear electronic susceptibility )((-C0A, COL,COL,--COS)of liquids; (r) and (i) stand for the real and imaginary part of
)(, respectively. 2 L laser wavelength

Liquid 2L= 555 nm ~ 2L= 495 nm" 2e= 545 nm u

[1014 cm3/erg] [101. cma/erg] [101. cm3/erg] [1014 cm3/erg] [1014 cma/erg]

(r) (i) (r) (i) (r)

C6H 6 1.75_+0.15 2.2_+0.2 1.844-0.15 <0.02 0.544-0.05 <0.002 0.65 4- 0.07

C6H5C1 3.0 + 1.0
C6HsNO2 4.0 -+2.0
CS 2 8.7 -+0.8
CC14 1.1 4-0.1 2.64-0.2

a M.D. Levenson, N, Bloembergen: J. Chem. Phys. 6@, 1323 (1974).

b M.D.Levenson, N.Bloembergen: Phys. Rev. B 1@, 4447 (1974).

diamond the values of the three independent compo-
nents of the electronic nonlinearity (see Subsec. 1.2.1)
were determined by using different angles between the
polarization directions of the linearly polarized light
fields [24, 52]. The measured numbers are given in
Table 3. Large changes of the electronic nonlinearity
with frequency COl were found when the laser energy
hCOL was approximately half of the energy of the
indirect band gap of diamond (5.4 eV). These variations
and the measured imaginary part of the electronic
susceptibility for high laser frequencies (2hCOL_~6.08 eV)
imply contributions from two-photon absorption
(see Subsec. 1.2.2 ii).
Measurements on four cubic fluorides, CaF z, CdF 2,
SrF2, and BaF2, were carried out using the composite
crystal technique [24, 51]. With this technique the
electronic nonlinearity was measured relative to the
Raman susceptibility of the calcite 1088-cm-1 mode.
By combining the results with detailed investigations
of the polarization of the anti-Stokes beam the absolute
values for all three non-vanishing components of the
third-order electronic susceptibility have been deter-
mined [53]. The results are shown in Table 3. There is
an anharmonic oscillator model of Boling et at. [54]
where the third-order nonlinear susceptibility is cor-
related with the linear index of refraction and an
effective resonant frequency according to the Sell-
meyer equation. A comparison of the experimental
data with this model shows that the model describes
the qualitative trend of the experimental results [24].
In the papers discussed above usually the non-resonant
electronic susceptibility has been measured and cali-
brated in terms of the well-known Raman matrix
elements. In [25] spontaneous Raman parameters of
CaCO3 have been determined relative to electronic
susceptibility values which are known from other
experiments. In the experiments, a probe beam was
used with a frequency copr which was different from
the frequencies of the pump and Stokes beams, col
and COs,respectively, see also [26, 55, 56].

Table 3. Third-order nonlinear electronic susceptibility Ze(--COA,e)L, COL,--COS) of solids and Raman contribution N]e~x]Z/4hcto nonlinear
susceptibility; (r) and (i) stand for the real and imaginary part of )(, respectively. 2 L laser wavelength, A7 Raman frequency shift

Material )~L A7 Nl~Rxxl2/4hc Z~xx[1014 cm3/erg] )(eyyx[1014 crn3/erg] )~exyy[1014 cma/erg]

[nm] [cm-1] [1012 cmZ/erg]
(r) (i) (r) (i) (r)

Diamond 545 1332 56.2 + 6 b 4.60+ 0.6 b <0.04 ~ 1.72_+0.18 b < 0.005 b 1.84_+0.2 b
CaF 2 575 322 0.53+0.11 b 0.40_--t_-0.04" <0.02 b 0.17+0.02 a <0.01 b 0.204- 0.02 a
SrF 2 575 285 0.84_+0.27 b 0,52_+0.04" 0.07_+0.02 b 0.25_+0.02" 0.04_+0.01 b 0.27_+0.02"
CdF z 575 322 1.07 -I-0.25 b 1,49 4- 0.16" < 0.02 b 0.414- 0.05 a < 0.02 b 0.48 _+0.05 a
BaF 2 575 240 1.87_+0.36 b 0,69_+0.05" 0.3 _+0.1b 0.364-0.03" 0.06+0.02 b 0.404-0.03"

" R.T.Lynch, Jr., M.D. Levenson, N. Bloembergen: Phys. Lett. 50A, 61 (1974).
b M.D. Levenson, N. Bloembergen: Phys. Rev. B 10, 4447 (1974).
220 M. Maier
It should be noted that three-wave mixing has also
been observed in a silica fiber optical waveguide
[57-59]. Phase-matching was achieved by propagating
the light waves with frequencies COL, mS, and co4 in
different waveguide modes to balance bulk disper-
sion.
Very recently, Owyoung [60] has described a two-
beam nonlinear interferometric technique which per-
mits the measurement of the real and imaginary parts
of the third-order nonlinear susceptibility and a separa-
tion of the electronic and molecular contributions. A
strong pulsed pump beam induces a phase shift in
one arm of a Jamin interferometer, which is probed
with a cw dye laser. The results for liquid CS2 and
C 6 H 6 a r e compared with those of CARS and of different
methods. It is emphasized that the main problem in
the comparison is the lack of a common standard of
calibration that can be applied to all of the data.
2.2.2. Coherent Anti-Stokes Raman Scattering as a
Spectroscopic Tool
CARS is a new analytic spectroscopic technique. The
major advantages are the many orders of magnitude
of possible increase in sensitivity compared to spon-
taneous Raman scattering and its observation in a
spectral region Iargely free of fluorescence. It should
be noted that the fluorescence occurs predominantly
in the Stokes frequency region.
To demonstrate the sensitivity of CARS Begley et al.
[61, 62] investigated benzene-toluene mixtures over
a range of benzene concentrations from 50% to less
than 0.3%. The total nonlinear susceptibility of the
mixture is the sum of the contributions of the individual
components. Since the anti-Stokes intensity is related
to the square of the total susceptibility, see (25), inter-
ference terms between neighbouring Raman modes of
the components arise in addition to the usually
observed interference with the non-resonant suscepti-
bility. Using the linear dependence of the susceptibility
on the number density of molecules, see (19), it follows
from (25) that at high concentrations N~ of benzene
the Raman signal scales as N~. At low concentrations
it scales linearly with N B because of the cross terms
due to the nearby toluene line. The experiments were
carried out with a dye laser pumped by a frequency-
doubled N d : Y A G laser. The light beams of both
lasers were mixed in the liquid cell. Fig. 10a shows the
spectra of benzene at 50, 25, and 12.5 % concentration
in toluene. The measured Raman peak intensity ratios
IB/IT of the 992-cm- 1 benzene and 1003-cm- 1 toluene
@ (~ BENZENE-TOLUENE ~'
MIXTURES .~
IB/IT ,&//
50%
9100 /t
BENZENE
;: 12.5%
fl 10
.//,/"
,~ . ~ , ~ &
i i 1 1o too
i
No 9Bo ~9o ~ "~o l&O
(WL-~S)/2~c[cm-1] NBI N T
Fig. 10 (a) Coherent anti-Stokes Raman spectra of benzene-toluene
mixtures. (b) A plot of the benzene-toluenepeak signal ratios IB/IT
vs concentration NB/NT. At the very low concentrations residual
benzene in the solvent caused deviations from the expected linear
behaviour. The triangles represent data points corrected for a
residual benzene concentration of 0.17% [61]
lines are plotted in Fig. 10b versus concentration
NB/NT on a logarithmic scale. As predicted by theory,
the intensity varies as the square of the concentration
down to 10% and linearly at lower concentrations.
The linear scaling is important for practical applica-
tions since it allows measuring of smaller concentra-
tions than given by the N~ dependence. The ultimate
limit for measuring small concentrations is set by
the electronic nonlinear susceptibility of the solvent.
The development of an optical and electronic arrange-
ment for CARS with high sensitivity has been reported
in [-63]. The CARS spectrum of a dilute solution of
diphenyloctatetraene in benzene was measured with
a greater signal-to-noise ratio as compared to con-
ventional Raman techniques. Higher-order than four-
wave mixing processes were observed.
In principle, CARS appears particularly useful for
investigating biological compounds, where background
fluorescence is a problem for spontaneous Raman
studies. It has been shown, however, [64] that the
observed CARS spectral shape in liquid water differs
significantly from the corresponding spontaneous
Stokes Raman profile (solid and broken lines, respec-
tively, in Fig. 11). This is due to the interference be-
tween resonant Raman contributions and non-resonant
electronic contributions to the nonlinear susceptibility
(see Subsec. 1.2.2) which are of the same order of
magnitude in water. For quantitative studies of sub-
stances in aqueous solutions, it will be necessary,
therefore, to map out first the CARS spectrum of pure
water.
 Applicationsof StimulatedRaman Scattering
~I ~;o ~ I STOKESRAMAN
i the Raman-induced Kerr effect a strong circularly
21
0 frequency spectrum around the Stokes (or anti-Stokes)
2000 3000 4000
(t~L-~S)/2~c[cm4]
Fig. 11. CARS signal strength for liquid water versus Raman shift
(coL- cos)/2~c. The symbolsrepresent the experimentalpoints, the
solid line is a theoreticalcurve.The broken line corresponds to the
spontaneous StokesRaman spectrum of liquid water [64]
Since the nonlinear susceptibility is proportional to
the number density of molecules, see (19), coherent
anti-Stokes Raman scattering in gases has been used
to measure the H2 concentration and the temperature
in flames [65, 66]. The detection capability of the
method was tested by measuring the He concentration
in mixtures with N 2 [-65]. A detection sensitivity of
approximately 10 ppm H2 was found, which is due
to the contribution of the real electronic susceptibility
of N2. A measured calibration curve was used to map
the Hz number density profiles in a flame of natural
gas premixed with air.
Temperature measurements were carried out in a
flame from a burner using town gas [66]. Small
amounts of H2 (10 -3 concentration) were found in
the flame. When a Boltzmann equilibrium is established
in the flame the temperature can be determined from
the populations of different rotational and vibrational
levels of the H2 molecules. The population difference
NA between the levels connected by the Raman transi-
tions enters the nonlinear Raman susceptibility, see
(19). By measuring the ratio of the anti-Stokes powers
for two lines with different rotational quantum numbers
J in the ground-state fundamental band, the temper-
ature can be calculated. The temperatures measured
by CARS were in good agreement with thermocouple
values.
The measurements discussed in this section were
carried out using pulsed lasers. Recently, cw generation
of coherent anti-Stokes Raman radiation was observed
i n C H 4 gas using an argon laser and a tunable dye laser
pumped by the argon laser [67]. This is an important
experimental progress because cw lasers have the
221
advantage of better frequency and amplitude stability
in comparison with pulsed lasers.
In closing this section a new nonlinear technique for
measuring Raman spectra should be mentioned. In
polarized pump beam at frequency COL induces an-
isotropic changes in the refractive index only at Raman
shifted frequencies [68]. These changes are probed by
a weak linearly polarized light beam with a broad
frequency cos (or COA)-The changes of the refractive
index cause the probe beam to be partially transmitted
through a polarizer that normally blocks it. The
spectrum of the transmitted probe beam reflects the
spontaneous Raman spectrum.
2.3. Relaxation Times of Material Excitations
It has been shown in Subsec. 1.2.3 that there are two
characteristic times for the relaxation of molecular
vibrations: the phase relaxation time r, describing the
decay of the vibrational amplitude q, and the energy
relaxation time z', corresponding to the lifetime of the
first vibrational energy level. The measurement of
these relaxation times proceeds in two steps:
i) the excitation of molecular vibrations by SRS of a
first strong laser pulse; ii) the probing of the decay
of the molecular vibrations by anti-Stokes Raman
scattering of a second weak laser pulse delayed with
respect to the first one. The phase relaxation time z is
obtained by measuring the decay of the amplitude q
of the molecular vibrations by coherent anti-Stokes
Raman scattering; the energy relaxation time z' is
found by measuring the decrease of the population
N 1 of the first excited vibrational level by incoherent
anti-Stokes Raman scattering. First we draw our atten-
tion to the excitation of molecular vibrations by SRS,
then we discuss the probing of the decay of the vibra-
tions.
2.3.1. Excitation of Molecular Vibrations
When the molecular vibrations are driven in resonance
by the light fields (2) the following equations for the
amplitude q of the vibrations and the difference
NA = N o - N 1 in population of the ground and excited
states are obtained from (10) and (11) E2].
Oq 1 i ~o~ELE~ A (27)
o~ + 2 r q - 4coo
~ aq
&A i
s - A)= - --U (ELE~q* - E*Esq). (28)
& 4h oq
222 M. Maier

Here, we neglected the anti-Stokes field which is usually i i I

small compared to the Stokes field and assumed the
laser field to be constant. The molecular vibrations "~"~176
are coupled to the equation for the Stokes field E s
~.= "'"'".~/*
n #E s 0E s rCiosN 0e 6
--- + -- - ELq*. (29) t,..i "..
c Ot r cn ~3q C
.9
In order to find the time dependence of q and A the "~ . --

coupled Eqs. (27)-(29) have to be solved. The solution laJ

of the differential equations is simplified by the follow-
ing approximation. It is assumed that the population
difference is changed only slightly by the light fields l~ [ ". \
/
(A ~-const). In this case, (27) and (29) can be solved " tp/l: =2
without considering the coupling to (28). The solution 16 ~ _ " "I:'11; =4
is then introduced into (28) and the resultant equation /
is solved [69]. /
When the time duration of the exciting laser pulse is
I[ ~ I
of the order of the relaxation times or shorter, the full 0 2
time-dependent Eqs. (27) and (29) must be solved. A Time t/lp
transient solution has been given by several authors Fig. 12. Calculatednormalizedamplitudeq2 of the molecularvibra-
[-70-73]. It was found to be in good agreement with tions and normalizedpopulationN~ of the first excitedvibrational
experimental results for stimulated Brillouin scattering level (broken and solid lines, respectively)versus normalized time
[74, 75] and stimulated Raman scattering [-76-79]. A t/tp. tp is the duration of the Gaussian laser pulse (dotted line)
solution for the saturation range has been presented
in [80, 81] and compared with experimental results.
Using the transient solution of (27) and (29) the time- delayed coherent anti-Stokes Raman scattering z. As
dependent population difference N A was calculated described in the preceding Subsection, molecular
numerically for the generator case [69]. The results vibrations are coherently excited by SRS of a first short
are shown in Fig. 121. The dotted line represents the light pulse EL1 and subsequently decay freely (see
Gaussian laser pulse with duration tp. The square of Fig. 12). The decay of the vibrational amplitude q is
the calculated amplitude q2 of the vibrations and the measured by coherent anti-Stokes Raman scattering
population of the first excited vibrational level of a second light pulse EL2 properly delayed with
N 1 = N(1 - A)/2 are given by the broken and solid lines, respect to the first one [85].
respectively, q2 and N 1 a r e normalized to their peak The time-integrated coherent anti-Stokes signal S as
values. It should be noted that some time is needed to a function of delay time t D between EL1 and E m is
build up q and N1 to their peak values which are given by [86]
delayed compared to the peak value of the laser pulse
(t=0). At the end of the laser pulse, the material
S(to)oc ~ IEL2(t--tD)q(1, t)12dt. (30)
excitations decay freely with their relaxation times - ao

z = 1/F and z ' = 1IF'. The determination of z and z'

by probing the decay curves via anti-Stokes Raman
scattering is discussed in the following Sections [82, 83].
2.3.2. Phase Relaxation Time
The experimental method used in the measurements
of the phase relaxation time z may be called time-
Here, it is assumed that there is no phase mismatch
in the generation of the anti-Stokes light. When the
laser pulses are short compared to the dephasing time z
the generated anti-Stokes signal decays exponentially
with z for large time delays t o [-see (30) and Fig. 12],
allowing the direct determination of the dephasing
time z from the slope of the decay curve.

1 The author would like to thank Dr. A. Laubereau for making a A differentmethod for measuring the dephasing time has been
available Fig. 12. described in [84].
 Applications of Stimulated Raman Scattering
AMPLIFIERt~M.-LLA SERI
TO SCOPE TPF
"PFU
KDP21~C F2 TOSCOPE"--EI
l SP3 J
J_[,t ~ . . ~ liT~
~ sc E
~F4. F f rHH/A v ~ & O ~ -
x~- ~ 9 "VD TOSCO~] SP2 " 1
Fig. 13. Schematic of experimental system for measuring the dephas-
ing time ~ of molecular vibrations in liquids. Three light beams B1,
B2, and B3 interact in the sample LC; glass pieces make the fixed
delays FD and the variable delay VD (Filter: F; spectrometer: SP;
photodetector: P; two-photon fluorescence system: TPF) [85]
The experiments are usually carried out with pico-
second light pulses since the phase relaxation times
are short. The experimental system used by v o n d e r
Linde et al. [85] is shown in Fig. 13. It consists of a
mode-locked Nd-glass laser which is followed by an
optical shutter to cut a single picosecond pulse out
of the pulse train (pulse duration _~8 ps). The single
light pulse is amplified and partially converted
to the second-harmonic frequency (V-L2----2V'L1=
18 868 cm- 1).
The powerful incident light pulse B1 generates intense
molecular vibrations by SRS. Two beam splitters
provide two light pulses (B2, B3) of small intensity.
One pulse (B3) with variable time delay t o served as
probe pulse for the vibrational amplitude in the
medium. The second probe pulse (B2) with fixed time
delay was used as a reference signal to improve the
accuracy. The angles between the light beams were
chosen to fulfil the phase-matching condition. The
coherent anti-Stokes light was measured after passing
spectrometers with photomultipliers and oscillo-
scopes.
A typical example of the experimental results is shown
in Fig. 14. The anti-Stokes signal S(tD) of the probe
beam is plotted versus the delay time t o for liquid
nitrogen [87]. The maximum of the curve is delayed
with respect to the peak of the pump laser pulse (t o-- O)
because of the transient nature of the excitation of
molecular vibrations by SRS with picosecond light
pulses. There is good agreement between the experi-
mental points and the calculated solid line. From the
exponential tail of the anti-Stokes signal a phase
relaxation time of 75__ 8 ps is found for liquid N2. The
results of measurements in liquid C2HsOH , CH3CC13
223
LIO,UID N2
1 ~ T= 77 K
u3
d
z
(.9
10-1
LIJ
ot--
u3I
V-
z
10-2
] ; I I
0 10 200 300
DELAY TIME t D [psi
Fig. 14. Coherent anti-Stokes probe scattering signal S(to) in liquid
nitrogen versus delay time t D between pump and probe pulse [87]
[69], n-alkanes [88], and in solid CaCO 3 [89] are
given in Table 4. The dephasing times vary from
0.26 ps for C2HsOH to 75 ps for liquid N 2. The results
for the internal Alg-mode of the CO~- group in CaCO3
and for liquid N 2 given in E87, 89] differ from earlier
reported data [90, 91]. It is believed that the data
obtained with a single picosecond pulse [87, 89] are
more reliable than those measured with a train of
short light pulses [90, 91].
The Raman-active vibrations of liquid CC14, SIC14,
SnC14, and SnBr 4 with frequencies from 459 cm-1 to
221 cm-1 require a separate discussion [86, 92]. The
Raman lines consist of several overlapping components
because the tetrahalides contain several C1 or Br
isotopes leading to slightly different vibrational fre-
quencies (see Fig. 8). The information obtained from
the experiments depends on the details of the wave-
vector geometry. For non-selective k-matching inter-
ference effects of different isotopic species have been
observed. In contrast, the dephasing time of one in-
dividual molecular species in isotope mixtures with
natural abundances has been measured under a selec-
tive k-vector condition. The experimental results for
liquid CC14, SIC14, SnC14, and SnBr4 are shown in
Table 4. It should be noted that it was possible to
measure the dephasing time of liquid SnBr 4 where
the isotopic line structure cannot be resolved in
spontaneous Raman spectroscopy.
Fischer and Laubereau [93] have presented a simple
model based on a semiclassical collision theory for
the dephasing of vibrationally excited molecules in a
224 M. Maier

liquid. It is assumed that the measured dephasing relaxation time z', i.e.
time can be decomposed into two parts: the "pure
dephasing" time zph, caused by processes which do 1 -- 1 1
..}- - - (31)
not affect the excited state population, and the energy z "Cph "g'

Table 4. Measured phase and energy relaxation times z and ~', respectively; phase relaxation time % has been calculated from measured
R a m a n linewidth 6g according to (32). (Raman frequency shift: A 7; temperature: T)

T[K] Av-[cm- 1] z[ps] 57[cm - 1] L[ps ] z'[ps] z'/z

N2 77 2326 75 _+8a 0.067 ~ 79___8~ 1.5x 1012b 2 • 10 I~

(56-+ 10) x 1012c 7.5 x 10 i 1
C2HsOH 300 2928 20 a 0.26 d 20 + 5 e 77
28 _ 14f
22 _+ 5g
1440 40 g
28 + 14f
CH3CC13 300 2939 1.3_+ 0.6~ 4.9 e 1.1e 5.2_+ 0~8h 4
1450 4h
n-heptane 293 2900 6i 11.0-t- 1.5i 1.83
248 2900 14.0 j
203 2900 16.0 j
isodecane 293 2900 10.85
n-decane 293 2900 11i 16.05 1.45
248 2900 21.0 j
n-tridecane 293 2900 15 ~ 21.05 1.40
n-pentadecane 293 2900 18 ~ 24.55 1.36
1-heptene 293 2900 21.05
1-decene 293 2900 33.55
1, 6-heptadiene 293 2900 60.0 j
CC14 300 459 4.0-+ 0.50 3.8k
3.6_+0.4 k
SiC14 425 3.0+ 0.5 k ~ 2.8 k
SnC14 368 2.8 + 0.3 k ~ 2.5 k
SnBr 4 221 3.0+0.3 k
CDaOD 293 2200 25 + 10h
CaCO 3 295 1086 4.4 + 0.31 1.1-1.41 3.8~4.8 l
297 8.5 + 2 m
90 t086 8.7 _+0.7 ~ 0.681 7.8 _+0.9 l
100 19.1 _+4 m
Diamond 295 1332 2.9-+ 0.3" 1.65 - 2.2" 3.2~.4"
77 1332 3.4_+ 0.3" 1.48 ~ 3.6 n
GaP 300 361 5.5-+0.50

a A. Laubereau: Chem. Phys. Lett. 27, 600 (1974)

b W.F. Calaway, G. E. Ewing: Chem. Phys. Lett. 30, 485 (1975)
c S.R.J.Brueck, R . M . O s g o o d , Jr.: Chem. Phys. Lett. 39, 568 (1976)
a D . v o n der Linde, A.Laubereau, W. Kaiser: Phys. Rev. Lett. 26, 954 (1971)
A.Laubereau, D . v o n der Linde, W.Kaiser: Phys. Rev. Lett. 28, 1162 (1972)
f R.R. Alfano, S. L. Shapiro: Phys. Rev. Lett. 29, 1655 (1972)
g A. Laubereau, G. Kehl, W. Kaiser: Opt. Comm. 11, 74 (1974)
h A.Laubereau, L.Kirschner, W.Kaiser: Opt. Comm. 9, 182 (1973)
i Estimated from Fig. 2 of P.R. Monson, L. Patumtevapibal, K.J. K a u f m a n n , P. W. Robinson: Chem. Phys. Lett. 28, 312 (1974)
J P . R . M o n s o n , L.Patumtevapibal, K . J . K a u f m a n n , P . W . R o b i n s o n : Chem. Phys. Lett. 28, 312 (1974)
k A.Laubereau, G.Wochner, W.Kaiser: Phys. Rev. A 13, 2212 (1976)
l A. Laubereau, G.Wochner, W. Kaiser: Opt. C o m m . 14, 75 (1975)
m R.R.Alfano, S.L.Shapiro: Phys. Rev. Lett. 26, 1247 (1971)
A.Laubereau, D . v o n der Linde, W.Kaiser: Phys. Rev. Lett. 27, 802 (1971)
o A.Laubereau, D . v o n der Linde, W.Kaiser: Opt. C o m m . 7, 173 (1973)
 Applications of Stimulated Raman Scattering 225

The authors show that the pure dephasing time ~h TO SCOPE ,TO SCOPE
is caused by fluctuations of the vibrational frequencies
due to intermolecular interactions. The theoretical
results compare favorably with measured values for
several liquids. VD -- --F3
It should be noted that for strongly polarized spon- ~v
taneous Raman lines there exists a simple relation
between the Raman linewidth 57 and the dephasing F2 F4 TO SCOPE
time v. For a homogeneously broadened line of Lo- l,O El lYlIIIIIA __ B1 ~ I1
- e,, U VlllllllJ - ~ I~1
rentzian shape we get Vl FD RS
= (27zcfv-)- 1. (32)
Fig. 15. Schematic of experimental system for measuring the energy
Although in practical cases the Raman lines may be
relaxation time z' of molecular vibrations in liquids. The pump beam
broadened by additional processes, e.g. isotope effects B1 at 2-~ 1.06 gm and the probe beam B2 at 2---0.53 gm interact
as discussed above, measurements in several liquids in the Raman sample RS. (Glass rod for fixed optical delay: FD; glass
support the validity of (32) (compare columns 4 and 6 prisms for variable delay: VD; filter: F; photodetector: P) [69]
in Table 4).
2.3.3. Energy Relaxation Time
The experimental system for the measurements of the
The extensive literature on the measurements of energy energy relaxation time z' is similar to Fig. 13. The
relaxation times of molecular vibrations in gases has system is modified to allow the optimum detection
been reviewed in several papers (see e.g. [-94-96] and of the spontaneous anti-Stokes light (see Fig. 15). Since
references therein). A large variety of different methods there are no phase-matching requirements, the in-
has been used in the experiments. I would like to men- coherent anti-Stokes light is collected by a lens at 90~
tion here a series of investigations of diatomic mole- to the incident laser 1-69]. Varying the delay time be-
cules, e.g. H2, D2, 02, N2, etc., where stimulated Raman tween pump and probe pulse, the rise and decay of
scattering has been used for the excitation of the the excess population of excited molecules is observed.
vibrational levels [97-106]. The decay of the incoherent anti-Stokes signal is a
In this section we concentrate on the vibrational energy direct measure of the energy relaxation time ~'. A typical
relaxation times ~' of molecules (in the electronic example of the incoherent anti-Stokes signal Si"C(tl~)
ground state) in liquids. It has been found that for as a function of delay time tD is shown in Fig. 16 (solid
polyatomic molecules in the liquid phase the energy line) for the vu-vibration at 2939 cm -1 of liquid
relaxation times of the first excited vibrational level of
a normal vibration are in the picosecond range. The
experiments are carried out, therefore, with pico- I I I
second light pulses of mode-locked lasers. The first
c
.n
vibrational energy level of a well-defined normal mode (,t')
is excited above the thermal equilibrium value by J
.<
=15ps
stimulated Raman scattering of a first short pulse Z
(see Subsec. 2.3.1). An additional weak light pulse u')
serves as a probe pulse with a definite delay time with ,,<0, 10.-1
respect to the pumping laser pulse. The probe pulse
0 CH3CCI3:CC[4 e'k~.2ps
monitors the decay of the population Na of the first I--
u')
excited level via incoherent anti-Stokes Raman scat- I
VH= 2939cm -1
tering. It should be emphasized that incoherent anti- I.---
Z
.<
Stokes Raman scattering provides a measure of the 10-2 I I I
population Nt of the first excited state which decays 0 10 20 30
according to the energy relaxation time ~' (see Fig. 12). DELAY TIME tD[PS]
In contrast, coherent anti-Stokes Raman scattering is
Fig. 16. Incoherent anti-Stokes probe signats Si"C(to) of the vH-vibra-
determined by the coherent amplitude q of the mole-
tions (2939cm -1) versus delay time tD in various mixtures
cular vibrations, which relaxes with the dephasing CH3CCI 3 : CCI 4, Molefractions of CHaCCI3, x = 0.6([]), 0.8(9 and
time ~. 1.0(e) [1071
226
3000
"7
E per cent CC14 to pure CH 3CC13. All of the experimental
{.2
>.-
~'D
(.O
z 200C
LL.I
d in near resonant interactions.
1.1_1
ii
LI.I
o 1000
O
"L,I.
d [108]. More detailed investigations using a novel tech-
<
rr"
O CH3CCL3 CD30D CCl4
z 0
Fig. 17. Schematic of the normal vibrational modes of molecules
CH3CC13, CD3OD and CC1r Arrows indicate the investigated and
discussed near resonant interactions [107]
CH3CC13 [107]. From the slope of the exponential
decay a vibrational lifetime of z'=5.2_+0.8ps is de-
rived.
Laubereau et al. [107] investigated the decay channels
of the 2939 cm -~ vibration in liquid CH3CC13. As-
suming a decay via interaction of three CH3CC13
molecules the diagram of the normal mode frequencies
suggests the 5/~-bending mode at I450cm -1 as a
favorable decay channel (see Fig. 17). Near energy
resonance occurs when the vH-vibration at 2939 cm-
decays to 5u-modes at 1450 cm-1 of two other mol-
ecules. In fact, the measurement of the anti-Stokes
signal shifted by 1450 cm- t showed that the an-mode
is populated in agreement with the measured decay
time of the vn-mode. The model of the decay via triple
interaction was substantiated further by investigating
liquid mixtures of CH3CC13 and CD3OD or CCI 4.
It is evident from Fig. 17 that there is excellent energy
resonance for the energy of the vH-vibration at 2939
cm-~ of CH3CC13 to the vD-vibration at 2227 c m - t of
CD3OD and to the Vcl-vibration at 713 cm -1 of
CH3CC13. Again this mechanism could be confirmed
by monitoring the population of the vo-vibration of
CD3OD via incoherent anti-Stokes Raman scattering.
The experimental results are direct evidence of the
intermolecular energy transfer in liquids. Measure-
ments of the energy relaxation of the vn-vibration of
CH3CC13 in liquid mixtures with CC14 were carried
out, because the low vibrational energy states of CC1r
do not allow an energy resonant decay of the high
energy of the vn-vibration of CH3CC13. It was found
experimentally that the admixture of liquid CCt 4 in-
creases drastically the energy relaxation time T' of
M. Mater
CH3CC13 (see Fig. 16, broken lines). An increase by
a factor of 5.6 was measured by admixing 60 mole
data of the CH3CC13 system give strong evidence that
the vibrational energy of one CH3CC13 molecule
decays through energy transfer to two other molecules
Experiments on ethyl alcohol suggested that the v n-
vibration at 2928 cm -1 decays to the 6n-vibration
around 1450 cm- x via near energy resonant processes
nique have shown that the excited vn-vibration at
2928 cm -1 first establishes a quasi-equilibrium with
neighbouring CH-levels around 2900cm -1 within
roughly 1 ps [109]. These neighbouring levels include
states of the vn-vibration with vibrational quantum
number v = 1 and states of the an-vibration with v = 2.
The vibrational energy of these levels decays sub-
sequently relatively slowly with a time constant of
-c'= 22 ps to the 6n(v = 1) states around 1450 cm- 1.
The energy relaxation times of the C-H stretching
vibrations in a series of liquid hydrocarbons have been
measured by Monson et al. [88].
The results of the measurements of the energy relaxa-
tion times z' of polyatomic molecules in the liquid
state are presented in Table 4. It should be noted that
these times are extremely short, typically in the pico-
second range. We did not include the values on liquid
C 6 H 6 and C 6 D 6 by Griffiths et al. [110], because there
are considerable doubts on the correctness of the
method used in these measurements [-111, 112].
At present, most of the experimental investigations are
on polyatomic molecules. For liquids consisting of
diatomic molecules only precise measurements on the
vibrational energy relaxation time z' of liquid nitrogen
have been carried out. In diatomic molecules there is
one vibrational mode. Vibrational energy can be trans-
ferred to rotational and translational degrees of free-
dom. As a result, substantially longer vibrational life-
times are expected than in polyatomic molecules with
near resonant energy transfer.
Using an optical Schlieren method a lower limit of the
energy relaxation times z' of the first excited vibrational
level in liquid Na and 02 of 1 ms has been found in
[113, 114]. Measurements via incoherent anti-Stokes
Raman scattering yielded a value of z'= 1.5 s for liquid
nitrogen at 77 K [115, 116]. In addition, CO, 02, and
CH 4 dissolved in liquid nitrogen were studied [116].
The measured relaxation rates were found to be con-
sistent with a simple model which essentially treats
the liquid as a high density gas where isolated binary
 Applications of Stimulated Raman Scattering
collisions cause vibrational relaxation. Very recently,
an even longer value of the lifetime of the first vibra-
tional state in liquid nitrogen of r'=56-+ 10s was
reported. This value is radiatively limited [117].
It is interesting to compare the dephasing time z and
the energy relaxation time -c' in liquids. Table 4 shows
that the ratio z'/T ranges from 1.36 for n-pentadecane
to the enormous value of 7.5 x 101~ for liquid nitrogen.
The large values of z'/z in several liquids indicate that
completely different mechanisms are effective in dis-
turbing the phase and relaxing the energy of molecular
vibrations in these liquids.
2.3.4. Phonons and Polaritons
In this Subsection, we discuss measurements of the
relaxation times of the TO phonons in diamond and
of a polariton mode in GaP.
In diamond picosecond laser pulses excited the TO
phonons by SRS to an occupation number exceeding
the thermal equilibrium value at 300 K by more than
thirteen orders of magnitude [118]. The decay of the
phonons was monitored by coherent anti-Stokes
Raman scattering of a probe pulse with variable delay.
The measured lifetimes of the hot phonons of 2.9_+ 0.3 ps
and 3.4_+0.3ps at 295 and 77K, respectively, were
found to be in good agreement with the corresponding
values obtained from measurements of the spontaneous
Raman linewidth (see Table 4). The good agreement
suggests that hot phonons decay with the same time
constant as phonons excited at the low power levels
of spontaneous Raman experiments.
The polariton mode investigated in GaP had a wave-
vector of 2770 cm- ~ and a frequency of AT-~361 cm- 1,
i.e. it was close to the fundamental TO phonon fre-
quency of 367cm -1 of the GaP lattice [119]. From
the phase-matched anti-Stokes Raman scattering of
a probe pulse a lifetime of 5.5 +0.5 ps of the polariton
mode was inferred. It has been discussed in [120] that
this number is essentially the phonon lifetime because
of the small frequency separation of the polariton and
phonon modes.
2.4. Generation of Tunable Coherent Infrared Radiation
In this Section we concentrate on the discussion of
stimulated Raman scattering with tunable lasers and
on stimulated polariton scattering. It should be men-
tioned, however, that four-wave parametric processes
have also been used successfully for the generation
of tunable ultraviolet and infrared radiation [20,
121-124] and of superbroad light spectra with pico-
227
xLxSl XS2 XS3
I I I [ I )
1 2 3 4 5 6
x [~rnl
Fig. 18. Laser line, first, second, and third Stokes Raman lines. Varia-
tion of the laser wavelength 2L by 4- 200 c m - 1 gives the indicated
tuning range for the Stokes lines
second duration [125, 126]. Because of the vast size
of the subject stimulated spin-flip Raman scattering
has been excluded from the discussion. For recent
reviews of tunable coherent light sources and of spin-
flip Raman lasers the reader is referred to [127-129].
2.4.1. Stimulated Raman Scattering with Tunable Lasers
When high laser power is incident to a Raman-active
medium stimulated Raman scattering occurs with
several higher-order Stokes lines. For a laser wave-
length in the red or near infrared region of the spectrum
the Stokes lines are shifted by the fixed frequency ~oo
of the molecular vibrations further to the infrared
region [130]. In Fig. 18 an example is shown. Starting
with a laser wavelength of 2L= 700 nm and a frequency
shift of 4155 cm- 1 the first, second, third Stokes com-
ponents etc. appear at 0.987, 1.67, 5.49 gin, respectively.
When the frequency coL of the incident laser is tunable
within 4-200 cm-1 the first- and higher-order Stokes
frequencies vary by 4-200 cm-1 (see Fig. 18).
This method of generating tunable infrared light was
used first by Ambartsumyan et al. [131]. The frequency
of a Nd: YAG laser was tuned by + 100cm -1 with
a grating as the back mirror of the laser. The laser light
was shifted by SRS in liquid pyridine further to the
infrared region.
Subsequent work was carried out with powerful tunable
dye lasers as the exciting light sources [132]. Frey
and Pradere [133] used a dye laser oscillator-ampli-
fier- system pumped transversely by a ruby laser with
a peak power of 300 MW. Using three different dyes
they covered the spectral region from 14000 cm-1 to
9700 cm- 1 with peak powers of 20 to 60 MW. Stimu-
lated Raman light was generated with the dye laser
system in H 2 or CH4 gas with frequency shifts of 4155
and 2916 cm-1, respectively. The first Stokes lines of
these gases were tunable from 9700 to 5500 cm- 1 with
peak powers between 5 and 20 MW. The correspond-
228 M. Maier

- - - 6s6p 3P0,1,2 350

300
791,1nm~ p m 5s 5d 3D1,2,3
5o
250
3e
"T
E 200
O
150
BARIUM
1S o 3 100
Fig. 19. Simplified energy level diagram of barim'n. When the dye 50 ~l r~L
laser was tuned near 791.1nm, stimulated Stokes emission was
observed near 2.8 gm and 2.9 gm [134] I I I I I I I I 9
O0 5000 10000 15000 20 000
kp[cm-1]
ing tuning range of the second Stokes lines was from Fig. 20. Dispersion curve of LiNbO3 in the vicinityof the Al-sym-
5500 to 2300 c m - 1 with peak powers between 0.5 and metry 248-cm-t polariton mode. The dots correspond to ex-
2 MW. perimentally observed points [141]
In a different approach near resonant stimulated elec-
tronic Raman scattering in atomic vapors was used
to shift the wavelength of tunable dye lasers. Advantage strongly on its wave vector kp (see Fig. 20). The dis-
is taken of the large frequency shift ( ~ 1 x 104 to persion curve can be obtained from experimental in-
2 x 104 c m - t ) of the Raman lines and the high trans- vestigations of spontaneous or stimulated Raman
parency in the infrared region of the spectrum. Tunable scattering at smalI angles near the forward direction
stimulated Stokes emission was generated around (see e.g. [ 138]). The wave vector kp is varied by changing
2.9 gin in barium vapor with a ruby-pumped, oscillator- the angle O between the incident and scattered light.
amplifier dye laser by Carlsten and Dunn [134]. The When polaritons are excited by stimulated light scat-
relevant energy levels are shown in Fig. 19. The con- tering, the mixed phonon-photon character of the
version efficiency into the first Stokes line was as high polaritons leads to the emission of infrared light at the
as 40 % and the Raman energy as high as 30 mJ. The polariton frequency. By changing the wave vector of
Raman light was tunable over ~ 100 c m - 1. Saturation the polariton mode the frequency of the infrared light
effects at dye laser energies > 100 mJ and vapor pres- can be tuned. In this subsection only those experiments
sures > 0.2 Torr were observed. on stimulated polariton scattering are discussed which
Stimulated electronic Raman scattering in potassium
and caesium vapor has been investigated by Cotter GOLAY
et al. [135, 136]. The measurements in Cs vapor were DETECTOR
carried out with a dye laser oscillator-amplifier com-
bination pumped by t h e second harmonic of a ruby
laser. The output power of the dye laser system ranged
from 200 to 800 kW depending on the dye. Using three " b- LIGHT~
different Raman transitions of caesium, the tuning
ranges of the Raman emission were 2.5-4.75 p.m,
5.67-8.65gm, and 11.7-15gm with powers up to
25 kW, 7 kW, and 2 kW, respectively. The possibility
of using a Raman oscillator to obtain tunable infrared MONOCHROMATOR
light has been discussed in detail in [137].

2.4.2. Stimulated Polariton Scattering

The coupling between transverse optical lattice modes
and the electromagnetic field in a crystal leads to an
excitation of mixed phonon-photon character, the
polariton. The frequency e~p of the polariton depends
SPECTROMETER
Fig. 21. Schematic diagram of the experimentalsetup for stimulated
polariton scattering. L is a 50-cmfocal length lens, BS denotes beam
splitters, PD1 and PD2 are photodiodes, and D indicates diffusers
[142]
 Applications of Stimulated Raman Scattering
are connected to the generation of tunable infrared
light.
There have been several investigations of stimulated
polariton scattering in LiNbO3 [139-143]. Contin-
uously tunable infrared radiation from 60 to 200 gm
was observed by Johnson et al. [-142]. The experimental
setup is shown in Fig. 21. Opposite ends of an un-
coated a-axis LiNbO 3 crystal were polished fiat and
parallel to form a resonator for the scattered Stokes
light. Stimulated polariton scattering from the lowest
A 1-symmetry p olariton mode in LiNbO 3was generated
by a Q-switched ruby laser. The stimulated scattering
was accompanied by the emission of intense far infra-
red radiation, which was emitted under an angle
to the direction of the laser light and detected by a
golay detector. The wavelength 21 of the infrared light
was tuned by varying the angle O' between the ruby
laser light and the crystal surface normal. The measured
infrared power decreased from 3W at 200gm to
0.25 W at 60 gm (for a signal power of approximately
106 W) in good agreement with theory.
The tuning range of the infrared radiation was ex-
tended to longer wavelengths by Piestrup et al. [143].
Using a Nd:YAG laser and an external resonator with
highly reflecting mirrors for the Stokes light, far infra-
red radiation has been generated in a long LiNbO 3
crystal (length 5 cm). The tuning range covered the
wavelength region from 150 to 700grn with peak
powers in the kilowatt range.
The advantage of generating tunable radiation by
stimulated polariton scattering compared to other
methods include: one fixed frequency pump source,
no magnetic field, room temperature operation, simple
continuous tuning.
The excitation of polariton modes and the generation
of infrared light by beating externally generated pump
and signal light beams in quartz and GaP was reported
in [144] and [145-147], respectively. The coherent
infrared generation in GaP was applied to a series of
measurements of the linear and nonlinear optical
parameters in the polariton region [147, 148]. It should
be noted that tunable infrared light has also been
generated by optical mixing using the second-order
nonlinear susceptibility which has not been discussed
in this paper.
3. Summary
In the discussion of the applications of stimulated
Raman scattering the main emphasis has been given
to the following areas: gain measurements, coherent
anti-Stokes Raman scattering (CARS), excitation of
229
molecular vibrations and lattice waves, generation of
intense tunable infrared light.
Raman gain measurements allow the determination of
the shape and width of narrow Raman lines and of the
absolute Raman scattering cross section. Raman
parameters and nonlinear electronic susceptibilities
have been measured in gases, liquids, and solids using
CARS. The major advantages of CARS are its high
sensitivity and its observation in a spectral region
largely free of fluorescence. It has been successfully used
for concentration measurements in mixtures and for
temperature measurements in flames. The excitation of
molecular vibrations and lattice waves by SRS provides
a new method for measuring relaxation times of mol-
ecules and phonons. Detailed studies show that the
phase and energy relaxation times are often in the
picosecond range in liquids and solids. New informa-
tion is obtained on intermolecular vibrational energy
transfer in polyatomic molecules. Although there are a
large number of competing methods for the generation
of intense tunable infrared light, stimulated Raman
scattering from molecular vibrations with tunable
lasers and stimulated polariton scattering have the
important advantages of room temperature operation
and simple continuous tuning over a broad wavelength
region. These advantages make them a promising tool
for infrared spectroscopy.
References
1. N. Bloembergen: Amer. J. Phys. 35, 989 (1967)
2. W.Kaiser, M.Maier: In Laser Handbook, ed. by F.T.Arecchi
and E.O.Schulz-Dubois (North-Holland, Amsterdam, 1972)
Vol. 2, p. 1077
3. M.Schubert, B.Wilhelmi: Soy. J. Quant. Electr. 4, 575 (1974)
4. A.Z.Grasyuk: Soy. J. Quant. Electr. 4, 269 (1974)
5. Y.R.Shen: In Light Scatterin 0 in Solids, ed. by M.Cardona,
Topics in Applied Physics, Vol. 8 (Springer, Berlin, Heidelberg,
New York, 1975) p. 278
6. C.S.Wang: In Nonlinear Optics, ed. by H.Rabin, C.L.Tang,
Quantum Electronics, Vol. 1 (Academic Press, New York, 1975)
7. W.J.Jones, B.P.Stoicheff: Phys. Rev. Lett. 13, 657 (1964)
8. J.A.Duardo, F.M.Johnson, M.A.El~Sayed: Phys. Lett. 21, 168
(1966)
9. S.Dumartin, B.Oksengorn, B.Vodar: J. Phys. 28, C 1-99
(1967); J. Chim. Phys. Phys. Chim. Biol. 64, 235 (1967)
10. R.A.McLaren, B.P.Stoicheff: Appl. Phys. Lett. 16, 140 (1970)
11. P.Gadow, A.Lau, Ch.T.Thuy, H.J.Weigmann, W.Werncke,
K.Lenz, M. Pfeiffer: Opt. Comm. 4, 226 (1971)
12. A. Lau, M. Pfeiffer, P. Gadow, W. Werncke, K. Lenz, H. J. Weig-
mann: Opt. Comm. 4, 228 (1971)
13. R.R.Alfano, S.L.Shapiro: Chem. Phys. Lett. 8, 631 (1971)
14. W.Werncke, J. Klein, A. Lau, K Lenz, G.Hunsalz: Opt. Comm.
ll, 159 (1974)
15. V.Arkhipov, N.G.Basov, E.M.Belenov, B.N.Duvanov, E.P.
Markin, A.N. Oraevskii: JETP Lett. 16, 333 (1972)
230 M. Maier

S.H.Bauer, D.M.Lederman, E.L.Resler, Jr., E.R.Fisher: In- 56. S.A.Akhmanov, N.I.Koroteev, A.I.Kholodnykh: J. Ram.
tern. J. Chem. Kinetics 5, 93 (1973) Spectr. 2, 239 (1974)
16. J.Lukasik, J.Ducuing: Phys. Rev. Lett. 28, 1155 (1972) 57. R.H.Stolen, J.E.Bjorkholm, A.Ashkin: AppI. Phys. Lett. 24,
17. V.S.Butylkin, G.V.Venkin, L.L.Kulyuk, D.I.Maleev, V.P. 308 (1974)
Protasov, Yu. G. Khronopulo: JETP Lett. 19, 253 (1974) 58. R.H.Stolen: IEEE J. Quant. Electr. 11, 100 (1975)
18. S.Kimel, A.Ron, S.Speiser: Chem. Phys. Lett. 28, 109 (1974) 59. R.H.Stolen, W.N.Leibolt: Appl. Opt. lg, 239 (1976)
19. H.Mennicke: Phys. Lett. 37A, 381 (1971) 60. A.Owyoung: Opt. Comm. 16, 266 (1976)
20. P.P. Sorokin, J. R. Lankard: IEEE J. Quant. Electr. 9, 227 (1973) 61. R.F.Begley, A.B.Harvey, R.L.Byer: Appl. Phys. Lett. 25, 387
21. N.Bloembergen: Nonlinear Optics (W.A.Benjamin, New York (1974)
1965) 62. R.F.Begley, A.B.Harvey, R.L.Byer, B.S.Hudson: J. Chem.
22. M.Schubert, B.Wilhelmi: Einj~hrung in die nichtlineare Optik Phys. 61, 2466 (1974)
Teil I (Teubner, Leipzig 1971) 63. I.Chabay, G.K.Klauminzer, B.S.Hudson: Appl. Phys. Lett.
23. P.D.Maker, R.W.Terhune: Phys. Rev. 137, A 801 (1965) 28, 27 (1976)
24. M.D.Levenson, N.Bloembergen: Phys. Rev. B10, 4447 (1974) 64. I.Itzkan, D.A.Leonard: Appl. Phys. Lett. 26, 106 (1975)
25. S.A.Akhmanov, N. I. Koroteev: Sov. Phys. JETP 40, 650 (1975) 65. P.R. R6gnier, J. P. E. Taran: Appl. Phys. Lett. 23, 240 (1973)
26. J.A.Giordmaine, W.Kaiser: Phys. Rev. 144, 676 (1966) 66. F. Moya, S. A. J. Druet, J. P. E. Taran: Opt. Comm. 13, 169 (1975)
27. M.Maier, W.Kaiser, J.A.Giordmaine: Phys. Rev. 177, 580 67. J.J.Barrett, R.F.Begley: Appl. Phys. Lett. 27, 129 (1975)
(1969) 68. D. Heimann, R. W. Hellwarth, M. D. Levenson, G. Martin: Phys.
28. N.Bloembergen, P.Lallemand: In Physics of Quantum Elec- Rev. Lett. 36, 189 (1976)
tronics, ed. by P. L. Kelley, B. Lax, P. E. Tannenwald (McGraw- 69. A.Laubereau, D. yon der Linde, W. Kaiser: Phys. Rev. Lett. 28,
Hill Book Co., New York 1966) p. 137 1162 (1972)
29. P.Lallemand, N. Bloembergen: Appl. Phys. Lett. 6, 210 (1965); 70. R.L.Carman, F.Shimizth C.S.Wang, N.Bloembergen: Phys.
ibid. 212 (1965) Rev. A2, 60 (1970)
30. N.Bloembergen, G.Bret, P.Lallemand, A.Pine, P.Simova: 71. S.A. Akhmanov, K. N. Drabovich, A. P. Sukhorukov, A. S. Chir-
IEEE J. Quant. Electr. 3, 197 (1967) kin: Soy. Phys. JETP 32, 266 (1971)
31. P.Lallemand, P.Simova, G.Bret: Phys. Rev. Lett. 17, 1239 72. N.M.Kroll, P.L.Kelley: Phys. Rev. A4, 763 (1971)
(1966) 73. T.vonFoerster, R.J.Glauber: Phys. Rev. A3, 1484 (1971)
32. P.Lallemand, P.Simova: J. Mol. Spectr. 26, 262 (1968) 74. M.Maier, G.Renner: Opt. Comm. 3, 301 (1971)
33. G.Bisson, G. Mayer: Compt. Rend. Acad. Sci. 265, 397 (1967); 75. K.Dar~e, W.Kaiser: Phys. Rev. Lett. 26, 816 (1971)
J. Phys. 29, 97 (1968) 76. R.L.Carman, M.E.Mack: Phys. Rev. A5, 341 (1972)
34. S.R.J.Brueck, A.Mooradian: Opt. Comm. 8, 263 (1973) 77. W.H. Lowdermilk, G. I. Kachen: Appl. Phys. Lett. 27, 133 (1975)
35. C.S. De Silets, C.K.N. Patel: Appl. Phys. Lett. 22, 543 (1973) 78. M. Chatelet, B.Oksengorn: Chem. Phys. Lett. 36, 73 (1975)
36. I.Reinhold, M.Maier: Opt. Comm. 5, 31 (1972) 79. R.S. Adrain, E.G.Arthurs, W.Sibbett: Opt. Comm. 15, 290
37. H. G6rner, M. Maier, W. Kaiser: J. Raman Spectr. 2, 363 (1974) (1975)
38. R.H.Stolen, E.P.Ippen: Appl. Phys. Lett. 22, 276 (1973) 80. K.Dar6e, W.Kaiser: Opt. Comm. 10, 63 (1974)
39. B.E.Kincaid, J.R.Fontana: Appl. Phys. Lett. 28, 12 (1976) 81. K.Dar6e: Opt. Quant. Electr. 7, 263 (1975)
40. W.G.Rado: Appl. Phys. Lett. 11, 123 (1967) 82. A.Laubereau, W.Kaiser: Opto-Electronics 6, 1 (1974)
41. F. De Martini, F.Simoni, E.Santamato: Opt. Comm. 9, 176 83. A.Laubereau, W.Kaiser: Ann. Rev. Phys. Chem. 26, 83 (1975)
(1973) 84. F.Capasso, F.De Martini: Opt. Comm. 9, 172 (1973)
42. M.D. Levenson, N. Bloembergen: J. Chem. Phys. 60, 1323 (1974) 85. D.von der Linde, A.Laubereau, W.Kaiser: Phys. Rev. Lett. 26,
43. R.T. Lynch, Jr., S. D. Kramer, H. Lotem, N. Bloembergen: Opt. 954 (1971); see also D.von der Linde: Appl. Phys. 2, 281 (1973)
Comm. 16, 372 (1976) 86. A.Laubereau, G.Wochner, W.Kaiser: Phys. Rev. A 13, 2212
44. T.Yajima: J. Phys. Soc. Japan 21, 1583 (1966) (1976)
45. J.J.Wynne: Phys. Lett. 29, 650 (1972) 87. A.Laubereau: Chem. Phys. Lett. 27, 600 (1974)
46. E.Yablonovitch, C. Flytzanis, N. Bloembergen: Phys. Rev. Lett. 88. P.R. Monson, L. Patumtevapibal, K.J. Kaufmann, P. W. Robin-
29, 865 (1972) son: Chem. Phys. Lett. 28, 312 (1974)
47. S.D.Kramer, F.G. Parsons, N.Bloembergen: Phys. Rev. B9, 89. A.Laubereau, G.Wochner, W.Kaiser: Opt. Comm. 14, 75
1853 (1974) (1975)
48. C.K.N.Patel, R.E.Slusher, P.A.Fleury: Phys. Rev. Lett. 17, 1011 90. R.R.Alfano, S.L.Shapiro! Phys. Rev. Lett. 26, 1247 (1971)
(1966) 91. R.R. Alfano, S. L. Shapiro: In Phonons, ed. by M. A. Nusimovici
49. J.J.Wynne: Phys. Rev. 178, 1295 (1969) (Flammarion, Paris 1971)
50. E.Yablonovitch, N.Bloembergen, J.J.Wynne: Phys. Rev. B3, 92. W.Kaiser, A.Laubereau: In Laser Spectroscopy, Proc. 2nd
2060 (1971) Intern. Conf., Meg6ve, 1975, ed. by S.Haroche, J.C.Pebay-
51. M.D.Levenson: IEEE J. Quant. Electr. 10, 110 (1974) Peyroule, T.W. Hiinsch, S. E. Harris: Lecture Notes in Physics
52. M.D. Levenson, C. Flytzanis, N. Bloembergen: Phys. Rev. B6, 43 (Springer, Berlin, Heidelberg, New York 1975) p. 380
3962 (1972) 93. S.F.Fischer, A.Laubereau: Chem. Phys. Lett. 35, 6 (1975)
53. R.T.Lynch, Jr., M.D.Levenson, N.Bloembergen: Phys. Lett. 94. E.Weitz, G.Flynn: Ann. Rev. Phys. Chem. 25, 275 (1974)
g0A, 61, (1974) 95. R.C.Amme: In Advances in Chemical Physics, ed. by J.Wm.
54. N.Boling, A.Owyoung, A.J.Glass: IEEE J. Quant. Electr. to McGowan (Wiley, New York 1975) Vol. 28, p. 171
be published 96. S.Ormonde: Rev. Mod. Phys. 47, 193 (1975)
55. S.A.Akhmanov, V.G.Dmitriev, A.I.Kovrigin, N.I.Koroteev, 97. F.De Martini, J.Ducuing: Phys. Rev. Lett. 17, 117 (1966)
V.G.Tunkin, A. I. Kholodnykh: JETP Lett. lfi, 425 (1972) 98. J. Ducuing, C. Joffrin, J. P. Coffinet: Opt. Comm. 2, 245 (1970)
 Applications of Stimulated Raman Scattering
99. M.A.Kovacs, M.E.Mack: Appl. Phys. Lett. 20, 487 (1972)
100. R. Frey, J. Lukasik, J. Ducuing: Chem. Phys. Lett. 14, 514 (1972)
101. J.Lukasik, J.Ducuing: Chem. Phys. Lett. 27, 203 (1974)
102. M.M.Auclibert, C.Joffrin: Opt. Comm. 5, 218 (1972)
103. M.M.Audibert, C.Joffrin, J.Ducuing: Chem. Phys. Lett. 19,
26 (1973)
104. M.M.Audibert, C.Joffrin, J.Ducuing: Chem. Phys. Lett. 25,
158 (1974)
105. M.M.Audibert, R.Vilaseca, J.Lukasik, J.Ducuing:Chem. Phys.
Lett. 31, 232 (1975)
106. M.M. Audibert, R. Vilaseca, J. Lukasik, J. Ducuing: Chem. Phys.
Lett. 37, 408 (t976)
107. A.Laubereau, L.Kirschner, W.Kaiser: Opt. Comm. 9, 182
(1973)
108. R.R.Alfano, S.L.Shapiro: Phys. Rev. Lett. 29, 1655 (1972)
109. A.Laubereau, G. Kehl, W.Kaiser: Opt. Comm. 11, 74 (1974)
110. J.E. Griffiths, M. Clerc, P. M. Rentzepis: J. Chem. Phys. 60, 3824
(t974)
111. A.Laubereau: J. Chem. Phys. 63, 2260 (1975)
112. J.E. Griffiths, M. Clerc, P. M. Rentzepis: J. Chem. Phys. 63, 2262
(1975)
113. G.Renner, M.Maier: Chem. Phys. Lett. 28, 614 (1974)
114. G.Renner, M.Maier: Chem. Phys. Lett. 35, 226 (1975)
115. W.F.Calaway, G.E.Ewing: Chem. Phys. Lett. 30, 485 (1975)
116. W.F.Calaway, G.E.Ewing: J. Chem. Phys. 63, 2842 (1975)
117. S.R.J.Brueck, R.M.Osgood, Jr.: Chem. Phys. Lett. 39, 568
(1976)
118. A.Laubereau, D. von der Linde, W.Kaiser: Phys, Rev. Lett. 27,
802 (1971)
119. A.Laubereau, D.von der Linde, W.Kaiser: Opt. Comm. 7, 173
(1973)
120. P.G.Harper: Opt. Comm. i0, 68 (1974)
121. P.P.Sorokin, J.J.Wynne, J.R.Lankard: Appl. Phys. Lett. 22,
342 (1973)
122. J.J. Wynne, P. P. Sorokin, J. R. Lankard: In Laser Spectroscopy,
ed. by R.G.Brewer and A.Mooradian (Plenum, New York,
1974) p. 103
231
123. A.H.Kung: Appl. Phys. Lett. 25, 653 (1974)
124. I.L.Tyler, R.W.Alexander, R.J.Bell: Appl. Phys. Lett. 27, 346
(1975)
125. A. Penzkofer, A. Laubereau, W. Kaiser: Phys. Rev. Lett. 31, 863
(1973)
126. A. Penzkofer, A.Seilmeier, W.Kaiser: Opt. Comm. 14, 363
(1975)
127. J. Kuhl, W. Schmidt: Appl. Phys. 3, 251 (1974)
128. H.G.H~ifele: Appl. Phys. 5, 97 (1974)
129. M.J. Colles, C. R. Pidgeon: Rep. Progress in Phys. 38, 329 (1975)
130. M.D.Martin, E.L.Thomas: Brit. J. Appl. Phys. 18, 1739 (1967)
131. R.V.Ambartsumyan, V.M.Apatin, V.S.Letokhov: JETP Lett.
15, 237 (1972)
132. W.Schmidt, W. Appt: Z. Naturf. 27a, 1373 (1972)
133. R. Frey, F. Pradere: Opt. Comm. 12, 98 (1974)
134. J.L.Carlsten, P.C.Dunn: Opt. Comm. 14, 8 (1975)
135. D.Cotter, D.C.Hanna, P.A.K~irkk~iinnen, R.Wyatt: Opt.
Comm. 15, 143 (1975)
136. D.Cotter, D.C.Hanna, R.Wyatt: Opt. Comm. 16, 256 (1976)
137. D.Cotter, D.C.Hanna, R.Wyatt: Appl. Phys. 8, 333 (1975)
138. R.Claus, L.Merten, J.BrandmiJller: Light Scattering by Pho-
non-Polaritons, Springer Tracts in Modern Physics 75 (Sprin-
ger, Berlin, Heidelberg, New York 1975)
139. S.K.Kurtz, J.A.Giordmaine" Phys. Rev. Lett. 22, 192 (1969)
140. J. Gelbwachs, R.H. Pantell, H.E. Puthoff, J.M.Yarborough:
Appl. Phys. Lett. 14, 258 (1969)
141. J.M.Yarborough, S.S.Sussmann, H.E.Puthoff, R.H.Pantell,
B.C.Johnson: Appl. Phys. Lett. 15, 102 (1969)
142. B.C. Johnson, H.E. Puthoff, J.Soohoo, S.S. Sussmann: Appl.
Phys. Lett. 18, 181 (1971)
143. M.A. Piestrup, R.N. Fleming, R.H. Pantell: Appl. Phys. Lett.
26, 418 (1975)
144. S. Biraud-Laval, G.Chartier: Phys. Lett. 30A, 177 (1969)
145. F.De Martini: Phys. Lett. 30A, 319 (1969)
146. F.De Martini: Phys. Lett. 30A, 547 (1969)
147. F.De Martini: Phys. Rev. B4, 4556 (1971)
148. J.P.Coffinet, F.De Martini: Phys. Rev. Lett. 22, 60 (1969)