Dipole Polarizabilities of Diatomic Molecules

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Discussion Overview

The discussion revolves around calculating the components of the dipole polarizabilities, specifically αParallel and αPerpendicular, of polar diatomic molecules. Participants explore methods and procedures for these calculations, focusing on the application of external electric fields in different orientations.

Discussion Character

  • Technical explanation
  • Mathematical reasoning
  • Debate/contested

Main Points Raised

  • Samir inquires about the calculation of the components of dipole polarizabilities αParallel and αPerpendicular after calculating the static electric dipole polarizability αD.
  • Another participant asks how Samir calculated αD, prompting further details about the method used.
  • Samir explains using finite field theory with an external electric field strength of 0.005 a.u., noting that the molecule is aligned along the z-axis.
  • One participant suggests that if the z-axis aligns with the bond axis, αParallel is calculated, and to find αPerpendicular, the field should be applied perpendicular to the bond axis.
  • Samir seeks clarification on the specific calculation procedure for obtaining these components.
  • Another participant asks if Samir is using a computational program for the calculations.
  • Samir confirms the use of the computational chemistry package Molpro.
  • A participant mentions that there may be an option in Molpro to specify the orientation of the electric field.
  • Another participant suggests a command in Molpro that may be relevant for specifying the electric field orientation.

Areas of Agreement / Disagreement

Participants generally agree on the method of applying external electric fields along different axes to calculate the components of dipole polarizabilities. However, the specific procedures and commands for implementation in Molpro remain somewhat unclear and are still being discussed.

Contextual Notes

There are limitations regarding the clarity of the computational procedures and the specific commands in Molpro, which have not been fully resolved in the discussion.

sams
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Hello Everyone,

I have been recently calculating the static electric dipole polarizability αD of a polar diatomic molecule, but I was wondering how to calculate the components of the dipole polarizabilities αParallel and αPerpendicular of diatomic molecules? Any help is really appreciated.

Thank you very much for your time and consideration...

Regards,
Samir
 
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So how did you calculate ##\alpha_D##?
 
Using finite field theory by applying 0.005 a.u. external electric field strength. The molecule is taken along the z-axis and the calculated dipole polarizability is static. If we want to calculate the components we have to apply an external electric field along each of the three dimensional axis, and then? How can these components be calculated individually?
 
If the z-axis coincides with the bond axis, you calculated alpha_parallel. If you want the perpendicular part, you should chose the field perpendicular to the bond axis.
 
Exactly! But what is the procedure (calculation) to obtain these components?
 
Are you using some program?
 
Computational Chemistry package Molpro.
 
It's 15 years at least since I used molpro. Isn't there some option to specify the orientation of the electric field?
 
I think this is it: DIP,xfield,yfield,zfield;
 

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