Molecular Geometry and Rotational Constant Analysis

Dr. Yukio Yamaguchi

Center for Computational Quantum Chemistry, University of Georgia
with additions and modifications by T. Daniel Crawford, Virginia Tech

1. Read the molecular cartesian coordinates and atomic numbers from the given file.

2. Calculate all possible interatomic distances, Ri j .

q
Ri j = (Xi − X j )2 + (Yi −Y j )2 + (Zi − Z j )2 (1)

3. Calculate all possible bond angles. For example, the angle, φi jk , between atoms i − j − k, where j
is the central atom is given by:
cos φi jk = eji · ejk (2)
where the eij are unit vectors between the atoms, e.g.,

eXij = − Xi − X j /Ri j eYij = − Yi − Y j /Ri j eZij = − Zi − Z j /Ri j

(3)

4. Calculate all possible out-of-plane angles. For example, the angle θi jkl for atom i out of the plane
containing atoms j − k − l (with k as the central atom) is given by:

ekj × ekl
sin θi jkl = · eki . (4)
sin φ jkl

5. Calculate all possible torsional angles. For example, the torsional angle τi jkl for the atom connec-
tivity i − j − k − l is given by:

(eij × ejk ) · (ejk × ekl )

cos τi jkl = (5)
sin φi jk sin φ jkl

Can you also determine the sign of the torsional angle?

6. Find the center of mass of the molecule.

∑i mi Xi ∑i miYi ∑i mi Zi
Xc.m. = Yc.m. = Zc.m. = , (6)
∑i mi ∑i mi ∑i mi
where mi is the mass of atom i and the summation runs over all atoms in the molecule.

7. Calculate elements of the moment of inertia tensor.

β2i + γ2i


Iαα = ∑ mi (7)
i

Iαβ = ∑ miαiβi, (8)

i
where α, β, and γ correspond to choices of x, y, and z (e.g., Ixy is one choice of Iαβ ).

1
 8. Diagonalize the inertia tensor to obtain the principal moments of inertia.

Ia ≤ Ib ≤ Ic (9)

9. Determine the molecular type:

• diatomic
• linear polyatomic
• asymmetric top
• symmetric top (prolate or oblate)
• spherical top

10. Determine the moments of inertia in amu.Å2 and g.cm2 and determine the rotational constants in
cm−1 and MHz.

A ≥ B ≥ C (10)
h h h
A = B = C = (11)
8π2 Ia 8π2 Ib 8π2 Ic

For more information see E.B. Wilson, J.C. Decius, and P.C. Cross, ‘Molecular Vibrations’, McGraw-
Hill, 1955.