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C3v Symmetry - BCl3

The infrared spectrum of BCl3 shows vibrational bands at 995, 480, and 244 cm-1, while Raman bands appear at 995,
471, and 244 cm-1. Is the geometry of the molecule trigonal pyramid (C3v) or trigonal planar (D3h)? Is your answer to
this question consistent with chemical bonding principles (VSEPR)? Assign symmetry labels to the vibrational bands
and identify the stretches and bends.

E C3 σv

CC3v := 1 −1A : R C3v := 2 Γ uma := 1 Γ bonds := 0

1 1 1 A1: z, x2 + y2, z2 1 4 3
1
2 0 E: (x,y), (R ,R ), 3 2 1
2 z

−1 x y

(x2 + y2, xy)(xz,yz)

〈〉 〈〉 〈〉

 
 
 
 
 
 ∑ C3v
T 1 T 2 T 3
A1 := CC3v A2 := CC3v E := CC3v h :=

→
()Τϕ /Φ1 16.5 Τφ Γ0.606
tot = ( 0
12 00 12 180 526.8898
Γ vibΤµ
:= ()
T
Γ tot := Γ uma⋅ A1 + E ) Γ tot − A1 − A2 − 2 ⋅E

→
〈〉
∑ 
 

T i

0A : R
C3v⋅ CC3v ⋅Γ vib 2 A1: z, x2 + y2, z2
i := 1 ..3 Vib i := Vib =
2E: (x,y), (R ,R ),
2 z
h
x y

(x2 + y2, xy)(xz,yz)

→
〈〉
CC3v
∑ C3v⋅  T i

0A : R
⋅Γ stretch 1 A1: z, x2 + y2, z2
Γ stretch := Γ bonds Stretchi := Stretch =
1E: (x,y), (R ,R ),
2 z
h
x y

(x2 + y2, xy)(xz,yz)

→
〈〉
∑ 
 

T i

0A : R
C3v⋅ CC3v ⋅Γ bend 1 A1: z, x2 + y2, z2
Γ bend := Γ vib − Γ stretch
Bend i := Bend =
1E: (x,y), (R ,R ),
2 z
h
x y

(x2 + y2, xy)(xz,yz)

This analysis predicts that there should be 4 IR and 4 Raman active vibrations. It also predicts that the IR and Raman
vibrations should be coincident. This is not in agreement with the experimental data, so BCl 3 does not have trigonal
pyramidal geometry.

This analysis also predicts that the stretches should have A1 and E symmetry, but since it has already been concluded
that the molecule does not have C3v symmetry this result will not be discussed further.

D3h Symmetry - BCl3

E C3 C2 σh S 3 σv

    
1 1 1 1 1 1 A1': x2 + y2, z2 1 4 3
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1 −1 2 1 0

1 1 1 1 1 1 A1': x2 + y2, z2 1 4 3

2 1
−1 0
−1 1 1
−1

A2': Rz
3 2 1
1 −1 1 4 3
2 0 E': (x,y), (x - y , xy)
2 2
CD3h := A1": D3h := Γ uma := Γ bonds :=
1 1 −1 −1

1 1 −1 −1 −1 1A2": z
2 1 0
2 −1 0 −2 1 0E": (Rx, Ry), (xz, yz) 3 2 1
〈〉 〈〉 〈〉 〈〉

 
 
 
 
 
 
 

T 1 T 2 T 3 T 4
A1 := CD3h A2 := CD3h E := CD3h A11 := CD3h

〈〉 〈〉 →

 
 
 
 ∑ D3h ()Τϕ /Φ1 16.5 Τφ 0.606
T 5 T 6
A21 := CD3h E1 := CD3h h := Γ tot := Γ uma⋅ A21 + E

T
Γ tot = ( 12 0 −2 4 −2 2 ) Γ vib := Γ tot − A2 − E − A21 − E1 i := 1 ..6

Γ stretch := Γ bonds Γ bend := Γ vib − Γ stretch

→ → 
T 〈〉 〈〉 T 〈〉
∑ 
 
 ∑ D3h⋅
CD3h
 ∑ 
 

i T i i
D3h⋅ CD3h ⋅Γ vib ⋅Γ stretch D3h⋅ CD3h ⋅Γ bend
Vib i := Stretchi := Bend i :=
h h h

0 A2': Rz
1 A1': x2 + y2, z2

0A2': Rz 0A2': Rz
1 A1': x2 + y2, z2 0 A1': x2 + y2, z2

2E': (x,y), (x - y , xy) 1 E': (x,y), (x - y , xy) 1E': (x,y), (x - y , xy)
0 A1":
2 2

0A1": 0A1":
2 2 Stretch = 2 2
Vib = Bend =

1A2": z 0 A2": z 1A2": z

0E": (Rx, Ry), (xz, yz) 0 E": (Rx, Ry), (xz, yz) 0E": (Rx, Ry), (xz, yz)
This analysis shows that there are 3 IR active modes (2E', A2") and 3 Raman active modes (A1', E'). It also show that there
are two coincidences (2E'). Thus, D3h symmetry for BCl3 is consistent with the spectroscopic data.

Thus the specific assignments are: A1' = 471; A2" = 480; E' = 995; E' = 244. From the analysis above it can be seen that the
stretches occur at 995 and 471, and the bends are at 480 and 244 cm-1.

VSEPR theory would predict a trigonal planar arrangement of chlorine atoms around the electron deficient boron, so the
symmetry analysis and the bonding theory are in agreement with each other and the spectroscopic measurements.
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
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





→

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