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Vibrational Analysis: Dr. Mazhar Amjad Gilani

The document discusses vibrational analysis through frequency calculations in computational chemistry. It explains that frequency calculations are only valid at stationary points on a potential energy surface. The document outlines how to perform frequency calculations using keywords in computational chemistry software. It also discusses how frequency calculations can provide insights into normal modes, vibrational frequencies, zero-point energies, and thermal corrections to potential energy. Advanced topics covered include the relationship between estimated and exact Hessians and how the Hessian matrix relates atomic displacements to the curvature of the potential energy surface.

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63 views

Vibrational Analysis: Dr. Mazhar Amjad Gilani

The document discusses vibrational analysis through frequency calculations in computational chemistry. It explains that frequency calculations are only valid at stationary points on a potential energy surface. The document outlines how to perform frequency calculations using keywords in computational chemistry software. It also discusses how frequency calculations can provide insights into normal modes, vibrational frequencies, zero-point energies, and thermal corrections to potential energy. Advanced topics covered include the relationship between estimated and exact Hessians and how the Hessian matrix relates atomic displacements to the curvature of the potential energy surface.

Uploaded by

XarOon
Copyright
© © All Rights Reserved
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Part II

Vibrational Analysis

Dr. Mazhar Amjad Gilani

COMSATS University Islamabad, Lahore Campus

8-10-2018
Learning Objectives:

1. To be able to predict theoretical FTIR

2. To be able to characterize a stationary point


through Freq.
3. To be able to troubleshoot major problem in
Freq
4. To be able to predict the thermochemistry
application of mathematical
models and simulations to
chemical problems using
computers
Limitation of Energy Calculations & Optimization

Idealized view of nuclear position


Realistic View: Nuclei are in motion
Prior Geometry Optimization

Job Type (keyword)

Opt +Freq Keyword


Include Opt and Freq in the route section:
geometry optimization followed by frequency calculation

Same level of theory and basis set for opt and Freq
Frequency Calculation - Input
• keyword ‘freq’ requests a frequency calculation
• ‘hf/3-21G’ specifies level of theory for the calculation

• coordinates in Z-matrix format, but frequency calculations can


also be performed with cartesian coordinates
• structure must correspond to a stationary point
• recall, frequency calculations in harmonic approximation are
only valid at stationary points

8
Frequency Calculation - Output
in a frequency calculation we may want to determine:
• normal modes and vibrational frequencies

mode
frequencies in cm-
1

normal mode
displacements

9
Frequency Calculation - Output
in a frequency calculation we may want to determine:
• normal modes and vibrational frequencies
• zero-point vibrational energies

• thermal corrections to the potential energy

10
Tutorial: 01

TS is somewhat halfway between two minima


Computed Data

structure A (0) Kcal structure B (180) TS (90) B-A TS-A

-
-152.888887 -95943.89215 -152.88539 95941.6976 -152.881576 -95939.3 2.194507 4.587945
Tutorial: 02

Planar Vs. Pyramidal

TIP: Go to vibrations, select imaginary frequency and do manual displacement


Tutorial # 03: Plotting of FTIR
Example of Acetic Acid

Tutorial # 04: Thermochemistry Data


Example of Acetic Acid
Assignment: 3
Today’s Website
http://www.ccl.net/chemistry/
Vibrational frequencies are computed by determining the second derivatives of
the energy with respect to the Cartesian nuclear coordinates and then
transforming to mass-weighted coordinates. This transformation is only valid at
a stationary point. Thus, it is meaningless to compute frequencies at any
geometry other than a stationary point for the method used for frequency
determination.
For Advanced Level

Hessian: The matrix of second derivatives of energy with respect to displacement of


atoms

Estimated Vs. Exact Hessian

Estimated is done while doing optimization unless we specify CalcFC or CalcAll

Exact is done in Freq. calculations which calculates Hessian analytically


For Advanced Level

So how does one decide how to alter the atomic positions; that is, should a particular
bond be lengthened or shortened? If the derivative of the energy with respect to that
bond distance is positive, that means that the energy will increase with an increase in
the bond separation. Computation of all of the energy gradients with respect to the
positions of the nuclei will offer guidance then in which directions to move the atoms.
But how far should the atoms be moved; that is, how much should the bond distance
be decreased? The second derivatives of the energy with respect to the atomic
coordinates provides the curvature of the surface, which can be used to determine
just how far each coordinate needs to be adjusted. The collection of these second
derivatives is called the Hessian matrix, where each element Hij is defined as Hij ¼
@2E @q1@q2 , (1:53)
where qi is an atomic coordinate (say for example the y-coordinate of the seventh
atom).
Thanks a lot

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