GEOMETRY

OPTIMIZATION
By
Nandana Sailesh
II PG Chemistry
• The process of rearranging the geometry
of a molecule to minimize its energy.
• Characterization of stationary points on
PES.
• Stationary points are points on the PES
with
• The can be used to identify whether it’s a
minima or a saddle point.
• The optimized structure is closest in
geometry to the input structure.

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• For 1D PES (E-E0 = K(q-q0)2) can be used but
for multidimensional molecules complex
algorithms are necessary.
• of potential energy with respect to the
geometry gives the force constant
• Most modern geometry optimization only
include the 1st and 2nd derivatives of energy on
the PES.
• 1st derivative matrix is the gradient matrix
• The force constant matrix (2nd order derivative
matrix) is called a Hessian.
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 [ ] [ ]
𝜕 𝑞𝑖 1 𝜕 𝑞 01
g 𝜕 𝑞𝑖 2 𝜕 𝑞 02
𝑞𝑖= . 𝑞 0= .
. .
. .
𝜕𝑞𝑖𝑛 𝜕𝑞0𝑛

[ ]
𝜕2 𝐸 𝜕2 𝐸 𝜕2 𝐸
⋯
𝜕𝑞1𝜕𝑞1 𝜕𝑞1𝜕𝑞2 𝜕𝑞 1𝜕 𝑞𝑛
𝜕2 𝐸
𝐻= 𝜕𝑞2𝜕𝑞1
𝜕2 𝐸 𝜕2 𝐸
𝜕 𝑞 2𝜕 𝑞 2 𝜕 𝑞 2𝜕 𝑞𝑛
gi
⋮ ⋱ ⋮
𝜕2 𝐸 𝜕2 𝐸
⋯
𝜕 𝑞𝑛𝜕 𝑞 1 𝜕 𝑞𝑛𝜕 𝑞𝑛

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• Hessian is important for geometry optimization,
characterization of stationary point and vibration
calculations
• PES is not exactly quadratic, the first step/cycle doesn’t
give the optimized structure.
• We obtain q1 from qi and then use q1 as the input.
• The cycle will continue till there is not much
appreciable change in the geometry or gradient.

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