A Form of Susceptibility Tensors in

Crystalline Materials

All three-dimensional crystalline solids can be categorized into one of 32 different point-
groups, each of which is described by a unique set of symmetries. The 32 point groups
can be divided among 7 crystal systems: triclinic, monoclinic, orthorhombic, tetragonal,
trigonal, hexagonal and cubic.

The international notation, also called the Hermann-Mauguin notation, uses numbers
to describe rotational symmetry about the three principle axes, bars to represent point
inversion, and the letter “m” to denote mirror-symmetries. For example, the six point
groups that begin with “4” are symmetric when rotated by 90ı . D 360ı =4/ about the z
axis. Likewise, those that begin with “6” are symmetric when rotated by 60ı .D 360ı =6/
about the z axis. Point groups that begin with 4 look the same when rotated by 90ı and
then fully inverted (i.e., reflected through a point at the origin.) A letter “m” is appended
after each axis to denote a mirror symmetry plane that passes through the axis, and the
symbol =m indicates a mirror plane perpendicular to the axis.

An alternative, but equivalent form is the Schönflies notation, that uses the letters O,
T, C, S, and D to describe octohedral, tetrahedral, cyclic, mirror, and dihedral symmetry,
respectively. Integer subscripts are used to denote the multiplicity of each symmetry,
the subscripts “h” and “v” specify horizontal or vertical mirror planes.

Table A.1 summarizes the 32 crystallographic point groups and seven crystal systems,
and the two notations used to describe them. Eleven of the 32 groups are centrosymmet-
ric, meaning that the underlying crystal structure is invariant to a full inversion operation
of the form .x; y; z/ ! . x; y; z/. For these groups, it is easy to prove that all of
the even order susceptibility tensors mush vanish.

A-1
A-2 Susceptibility Tensors

A.1 Linear Susceptibility

In addition to summarizing the notation and terminology of point groups and crystal
classes, Table A.1 gives the form of the 33 linear susceptibility tensor ¦.1/ for each of
the 32 point groups. The cubic crystal systems are optically isotropic, meaning that the
linear susceptibility is proportional to the identity matrix. The tetragonal, trigonal, and
hexagonal crystal systems are uniaxial with the optic axis coinciding with the principle
crystallographic axis (the z direction of the crystal.) The triclinic, monoclinic, and
orthorhombic crystal systems are biaxial. As indicated in Table A.1, for the triclinic and
monoclinic systems, the linear susceptibility tensor is non-diagonal when expressed in
the crystallographic coordinate system.

A.2 Second-Order Nonlinear Susceptibility

In general, the second-order nonlinear susceptibility is a third-rank tensor that is de-
scribed by 27 complex elements, each of which is a function of two independent fre-
quency arguments. In crystalline solids, symmetry constraints typically allow one to
equate or eliminate many of these elements. Table A.2 specifies the form of the second-
order nonlinear susceptibility tensor j.2/
kl
, for the 21 non-centrosymmetric point groups.
In table A.2, solid lines are used to connect tensor elements that are constrained to
be equal to one another by virtue of crystal symmetry. Open and filled symbols that are
connected by a line are meant to show elements that are equal, but opposite in sign. The
numbers in italics next to each diagram give the number of non-zero elements in ¦.2/ ,
and the number in parentheses tells how many of these elements are independent.
In some cases, all of the interacting frequencies !1 , !2 and !3  !1 C !2 are far
separated from any resonant frequencies of the crystal. Under these conditions, one can
model the nonlinear susceptibility as lossless and dispersionless. That is, one can ignore
the frequency dependence and simply treat ¦.2/ as constant, third-rank tensor with real
elements. In this case, Kleinman symmetry applies, and the three cartesian subscripts can
be freely permuted. In table A.2, the dashed lines are used to connect tensor elements
that are equal (or opposite) when Kleinman symmetry applies. The square symbols
denote tensor elements that must vanish when Kleinman symmetry applies.
When describing second-harmonic generation, the nonlinear susceptibility tensor
depends on only one frequency argument, !1 D !2  !. In this special case, intrinsic
permutation symmetry dictates that the final two cartesian subscripts of j kl can be freely
interchanged. Under this condition, the last two indices can be contracted into a single
index m that ranges from 1: : :6. Table A.3 plots the form of the 36 susceptibility tensor
d for the 21 non-centrosymmetric point groups. As before, solid lines connect elements
that are equal (or opposite), dashed lines show elements that are equal under Kleinman
symmetry, and squares denote elements that vanish under Kleinman symmetry.

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 A.2. Second-Order Nonlinear Susceptibility A-3

Point Group ¦.1/ ¦.2/ ¦.3/

Centrosymmetric

Enantiomorphic

# independent

# independent

# independent
International

Sch ön flies

form of

# nonzero

# nonzero

# nonzero
Crystal ¦.1/

Polar
System
1 C1 9 6 27 27 81 81
Triclinic
1̄ C i / S2 9 6 - - 81 81
2 C2 5 4 13 13 41 41
Monoclinic m Cs 5 4 14 14 41 41
2/ m C 2h 5 4 - - 41 41
222 D2 3 3 6 6 21 21
Orthorhombic mm2 C 2v 3 3 7 7 21 21
mmm D 2h 3 3 - - 21 21
4 C4 3 2 13 7 41 21
4̄ S4 3 2 12 6 41 21
4/ m C 4h 3 2 - - 41 21
Tetragonal 422 D4 3 2 6 3 21 11
4mm C 4v 3 2 7 4 21 11
4̄2m or 4̄m2 D 2d 3 2 6 3 21 11
4 / mmm D 4h 3 2 - - 21 11
3 C3 3 2 21 9 73 27
3̄ S6 3 2 - - 73 27
Trigonal 32 or 321 or 312 D 3 3 2 10 4 37 14
3m or 3m1 or 31m C 3v 3 2 11 5 37 14
3̄m or 3̄m1 or 3̄1m D 3d 3 2 - - 37 14
6 C6 3 2 13 7 41 19
6̄ C 3h 3 2 8 2 41 19
6/ m C 6h 3 2 - - 41 19
Hexagonal 622 D6 3 2 6 3 21 10
6mm C 6v 3 2 7 4 21 10
6̄2m or 6̄m2 D 3h 3 2 4 1 21 10
6 / mmm D 6h 3 2 - - 21 10
23 T 3 1 6 2 21 7
m 3̄ Th 3 1 - - 21 7
Cubic 432 O 3 1 6 1 21 4
4̄3m Td 3 1 6 1 21 4
m 3̄m Oh 3 1 - - 21 4
Isotropic 3 1 - - 21 3

Table A.1: Summary of 32 crystal classes and point groups, showing the notation(s) and
the form of the linear susceptibility tensors.
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A-4 Susceptibility Tensors

Although it is only strictly valid for describing second-harmonic generation, the

contracted tensor d can also be used when the two frequency arguments !1 and !2 are
close enough that dispersion can be neglected, or when the conditions for Kleinman
symmetry apply.

A.3 Third-Order Nonlinear Susceptibility

In general, the third-order susceptibility is a fourth-rank tensor, described by 81 complex
elements which depend on three independent frequency arguments. The third-order
susceptibility tensor is non-zero for all 32 point groups, as well as for isotropic materials.
Symmetry arguments allow one to simplify the form of this tensor in most cases of
interest.
Table A.4 lists the non-zero elements of j klm for each of the 32 point groups, and
isotropic materials. The tensor elements are identified by their four cartesian subscripts,
and an over-bar is used to denote negation.
The numbers shown in italics indicate how many of the 81 elements are non-zero,
with the number in parentheses used to show how many independent quantities are
needed to completely specify all of the non-zero elements.
We note that these symmetry constraints apply to any third-order nonlinear process.
If some of the frequency arguments are equal to one another, or if the material is lossless,
then intrinsic permutation symmetry or full permutation symmetry can be used to further
constrain the form of the susceptibility tensor.
If the third-order susceptibility tensor is lossless and dispersionless (i.e., when Klein-
man symmetry applies), then the frequency arguments of ¦.3/ can be dropped, and the
cartesian subscripts can be freely permuted. When the order of subscripts does not mat-
ter, there are only 15 distinct ways to arrange the three cartesian indices x,y and z into
a group of four:
xxxx xxyy xxzz xxyz xxxz xxxy
yyyy yyzz yyyz yyxz yyxy (A.1)
zzzz zzyz zzxz zzxy

Table A.5 illustrates the form of ¦.3/ for the 32 crystal classes (and isotropic mate-
rials) for this more restrictive case when Kleinman symmetry applies. As in tables A.2-
A.3, solid lines connect elements that are equal (or opposite) to one another. Only the
15 elements listed in (A.1) are included, with the understanding that under Kleinman
symmetry the remaining 66 elements can be obtained by permuting the indices.

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 A.3. Third-Order Nonlinear Susceptibility A-5

xxx xyy xzz xyz xzy xzx xxz xxy xyx d11 d12 d13 d14 d14 d15 d15 d16 d16
Key: yxx yyy yzz yyz yzy yzx yxz yxy yyx = d21 d22 d23 d24 d24 d25 d25 d26 d26
zxx zyy zzz zyz zzy zzx zxz zxy zyx d31 d32 d33 d34 d34 d35 d35 d36 d36

Triclinic Trigonal

1 27(27) 3 21(9)

Monoclinic 32 10(4)

2 13(13)
3m 11(5)

m 14(14)
Hexagonal

6 13(7)
Orthorhombic

222 6(6)
6̄ 8(2)

mm2 7(7)
622 6(3)

Tetragonal 6mm 7(4)

4 13(7)

6̄2m 4(1)

4̄ 12(6)

Cubic

422 6(3) 23 6(2)

4mm 7(4) 432 6(1)

4̄2m 6(3) 4̄3m 6(1)

Table A.2: Form of j.2/

kl
for the 21 non-centrosymmetric point groups.

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A-6 Susceptibility Tensors

d11 d12 d13 d14 d15 d16

Key: d21 d22 d23 d24 d25 d26
d31 d32 d33 d34 d35 d36

Triclinic Cubic Trigonal

1 23 3

Monoclinic 432 32

2
4̄3m 3m

m
Tetragonal Hexagonal

4 6
Orthorhombic

222
4̄ 6̄

mm2
422 622

4mm 6mm

4̄2m 6̄2m

Table A.3: Form of the nonlinear susceptibility tensor d, in contracted notation, for the
21 non-centrosymmetric point groups.

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 A.3. Third-Order Nonlinear Susceptibility A-7

Triclinic Cubic
1, 1̄ (81 nonzero, independent elements) xxxx = yyyy = zzzz
23 xxyy = yyzz = zzxx yyxx = xxzz = zzyy
Monoclinic m 3̄ xyxy = yzyz = zxzx yxyx = xzxz = zyzy
xxxx yyyy zzzz xyyx = yzzy = zxxz yxxy = xzzx = zyyz
xxyy yyxx xxzz yyzz zzxx zzyy 21(7)
xyxy yxyx xzxz yzyz zxzx zyzy
2 xyyx yxxy xzzx yzzy zxxz zyyz xxxx = yyyy = zzzz
m 432
xxxz yyxz yxyz xyyz xxyy = yyzz = zzxx = yyxx = xxzz = zzyy
2/m 4̄3m
xxzx yyzx yxzy xyzy xyxy = yzyz = zxzx = yxyx = xzxz = zyzy
xzxx yzyx yzxy xzyy m 3̄m xyyx = yzzy = zxxz = yxxy = xzzx = zyyz
zxxx zyyx zyxy zxyy 21(4)
zzzx zzxz zxzz xzzz
41(41)
Isotropic
Orthorhombic xxxx = yyyy = zzzz
xxxx yyyy zzzz xxyy = yyxx = xxzz = yyzz = zzxx = zzyy
222
xxyy yyxx xxzz yyzz zzxx zzyy xyxy = yxyx = xzxz = yzyz = zxzx = zyzy
mm2 xyxy yxyx xzxz yzyz zxzx zyzy xyyx = yxxy = xzzx = yzzy = zxxz = zyyz
mmm xyyx yxxy xzzx yzzy zxxz zyyz ( xxxx = xxyy + xyxy + xyyx )
21(21) 21(3)

Tetragonal , Hexagonal*
xxxx = yyyy zzzz
4, 4̄, 4/m xxyy = yyxx xxzz = yyzz zzxx = zzyy 422, 4mm, 4̄2m, 4 / mmm 21(11)
41(21) xyxy = yxyx xzxz = yzyz zxzx = zyzy 622, 6mm, 6̄2m, 6 / mmm 21(10)
xyyx = yxxy xzzx = yzzy zxxz = zyyz
xyzz = yxzz xzyz = yzxz xzzy = yzzx
6, 6̄, 6/m
zzxy = zzyx zxzy = zyzx zxyz = zyxz
41(19)
xxxy = yyyx xxyx = yyxy
xyxx = yxyy yxxx = xyyy

* The hexagonal classes have the same nonzero elements as the

corresponding tetragonal classes, but with two additional constraints:
(xxxx = xxyy + xyxy + xyyx), (xxxy = yyxy + yxyy + xyyy)

Trigonal
xxxx = yyyy zzzz
xxyy = yyxx xxzz = yyzz zzxx = zzyy
xyxy = yxyx xzxz = yzyz zxzx = zyzy 32, 3m, 3̄m
xyyx = yxxy xzzx = yzzy zxxz = zyyz 37(14)
( xxxx = xxyy + xyxy + xyyx )
xxxz = yyxz = yxyz = xyyz xxzx = yyzx = yxzy = xyzy
3, 3̄ xzxx = yzyx = yzxy = xzyy zxxx = zyyx = zyxy = zxyy
73(27) yyyz = xxyz = xyxz = yxxz yyzy = xxzy = xyzx = yxzx
yzyy = xzxy = xzyx = yzxx zyyy = zxxy = zxyx = zyxx
xyzz = yxzz xzyz = yzxz xzzy = yzzx
zzxy = zzyx zxzy = zyzx zxyz = zyxz
xxxy = yyyx xxyx = yyxy xyxx = yxyy yxxx = xyyy
( xxxy = yyxy + yxyy + xyyy )

Table
08/29/2022 non-zero elements of the third-order susceptibility tensor j.3/
A.4: The21:32 klm
for each
of the the 32 point groups, and isotropic materials.
A-8 Susceptibility Tensors

xxxx xxyy xxzz xxyz xxxz xxxy

Key: yyyy yyzz yyyz yyxz yyxy
zzzz zzyz zzxz zzxy

Triclinic Tetragonal, Hexagonal*

4, 4̄, 4/m,
1, 1̄ 6, 6̄, 6/m

Monoclinic
422, 4mm, 4̄2m, 4 / mmm
2, m, 2/m
622, 6mm, 6̄2m, 6 / mmm

Orthorhombic Trigonal*

222, mm2, mmm 3, 3̄

Cubic, Isotropic*
23, m 3̄, 432, 4̄3m,
32, 3m, 3̄m
m 3̄m, isotropic

* The hexagonal, trigonal and isotropic cases obey the following

additional constraints:
(xxxx = 3xxyy), (xxxy = 3yyxy)

Table A.5: Form of the third-order susceptibility tensor for each of the 32 point groups
(and isotropic materials) in the case when Kleinman symmetry applies. Note that under
Kleinman symmetry, the four cartesian subscripts can be freely permuted, so that there
are at most 15 independent quantities needed to describe the tensor.

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