Lecture 33: Normal Coordinate Analysis
Lecture 33: Normal Coordinate Analysis
Lecture 33: Normal Coordinate Analysis
Normal coordinates are obtained from the solution of the eigenvalue problem,
z3
y3
r1 r2
z1 z2
y1 y2
f33 = bending �
• T •
2T = R G R
1
•
where R is the time derivative of the internal coordinates… the G matrix is
therefore a matrix of mass - weighted vector displacements of the atoms
with elements
Gtt = μ s t s t
where st is oriented in the direction in which atom is moving along internal
coordinate st over a unit distance. Thus, the time derivative taken twice of
atom , of reduced mass μ, displacing a distance st yields the KE.
3
st’ displacement of atom 2 to
internal coordinate
p31 p32
1 2
e31 e32
st displacement of atom 2 along
the internal coordinate
3
= [311 + 322 – (31 + 32)3] / r
p31 p31
1
Thus p311 – p313
r1 e31 0 e31 1
r2 = 0 e32 e32 2
r3 p31 p32 (p31 + p32 ) 3
r
r r
the S-matrix
multiplying out,
μ1 μ
(μ3 + μ1 )e31 e31 μ3e31 e32 r
e31 p31 + 3 e32 (p31 + p32 )
r
• μ1 μ
G = (μ3 + μ1 )e32 e32 e32 p32 + 3 e32 (p31 + p32 )
r r
μ1 μ1 μ3 2
r2
p31 p31 + 2 p32 p32 +
r r
(p31 + p32 )
a symmetric matrix
e31 e31 = e32 e32 = p32 p32 = p31 p31 = 1 unit displacements
μ3
μ3 + μ1 μ3 cos sin
r μ1 and μ3 are the
μ
G = μ3 + μ1 3 sin reciprocal masses of H
r and O, respectively.
2μ1 2μ3
+ 2 (1 cos )
r2 r
s1 (a1 ) 1 1
0 r1
� 2 2
s3 (a1 ) = 0 0 2 r2 �
�
s2 (b2 ) 1
1
0 �
2 2
this is a μ matrix�
Fsym = μ-1 F μ
Gsym = μ-1 G μ
f + f r 2f13 0
11 12
F sym = r 2f13 r2f33 0
0 0 f11 f22
2
μ3 (1 + cos ) + μ1 μ3 sin
0
r
2 2μ1 2μ
Gsym = μ3 sin + 23 (1 cos ) 0
r r2 r
0 0 μ3 (1 cos ) + μ1
G33 F 33 E 3 = 0
2 2
(
2 (G11 F11 + G22 F 22 + 2G12 F12 ) + G11 G22 G12 )(F 11 F12 F12 )=0
for H2O,
1
μ1 = μH = = 0.99206
1.008�
1�
μ3 = μ0 = = 0.06252
15.995�
r = 0.96 �
= 105�
= 42c2 2