3rd order energy perturbation correction

In summary, the conversation discusses deriving the general expression for the third-order perturbation energy in a non-degenerate quantum system. The equations for the nth order are given, and the solution for n=3 is shown. The next step is to find the interaction between the n=0,1,2,3 states and determine the value for <1|1>.
  • #1
valtorEN
36
0

Homework Statement



Derive the general expression of 3rd-order perturbation energy for a

non-degenerate quantum system.


Homework Equations



for nth order we have

(Ho-Eo)|n>+(H'-E1)|n-1> -E2\n-2>-En|0>=0 (given)

also,

<0|0>=1,

<1|0> = <0|1>=0,

<0|2>=<2|0>=-1/2<1|1>

<0|n>=<n|0>=-1/2*(<n-1|1>+<n-2|2>+...+<2|n-2>+<1|n-1>),

The Attempt at a Solution



for n=3 we get

(Ho-Eo)|3>+(H'-E1)|2>-E2|1>-E3|0>=0

now, multiply by <0| (this

we get <0|(H0-E0)|3> +<0|(H'-E1)|2>-<0|E2|1>-<0|E3|0>=0

by the rules above, the third term is = 0, the fourth is just =-E3 and the 2nd
is -1/2<1|1>

this gives E3=<0|(Ho-Eo)|3>-1/2*<1|(H'-E1)|1>

for <0|n>=<n|0>=-1/2(<n-1|1>+<n-2|2>+...+<2|n-2>+<1|n-1>)

for n=3

i get

E3=-1/2(<2|(H0-E0)|1>+<1|(H0-E0)|2>+<0|(H0-E0)|3>+<2|(H0-E0)|1>

+<1|(H0-E0)|2>)-1/2*(<1|(H'-E1)|1>) (phew!)

I am not sure what do do next

what is <1|2>=<2|1> = to?

i can see all the terms only have states 1 and 2 involved in them except the

3rd term <0|3> and the last term <1|1>, are these important?

does <1|1>=0?
 
Physics news on Phys.org
  • #2
you have to find the third order perturbation expansion for the energy correction, & not just the interaction between the n = 0,1,2 & 3 states.
 

Related to 3rd order energy perturbation correction

1. What is a 3rd order energy perturbation correction?

A 3rd order energy perturbation correction is a technique used in computational chemistry to improve the accuracy of electronic structure calculations. It involves calculating the energy of a system at the 3rd order level of perturbation theory and then using this value to correct the energy calculated at the 1st and 2nd order level.

2. Why is a 3rd order energy perturbation correction necessary?

Electronic structure calculations at the 1st and 2nd order level can be inaccurate, especially for systems with strong electron correlation. A 3rd order energy perturbation correction takes into account higher order effects and improves the accuracy of the calculated energy.

3. How is a 3rd order energy perturbation correction calculated?

The 3rd order energy perturbation correction is calculated using perturbation theory, which involves expanding the energy expression in terms of small parameters and then solving for the energy correction at the 3rd order level. This correction is then added to the calculated energy at the 1st and 2nd order levels.

4. What types of systems benefit the most from a 3rd order energy perturbation correction?

Systems with strong electron correlation, such as transition metal complexes, benefit the most from a 3rd order energy perturbation correction. This is because these systems have a large number of electrons that strongly interact with each other, making accurate energy calculations at the 1st and 2nd order levels difficult.

5. Are there any limitations to using a 3rd order energy perturbation correction?

One limitation is that the calculation of the 3rd order energy perturbation correction can be computationally expensive, especially for large systems. Additionally, this correction may not always improve the accuracy of the calculated energy, and in some cases, it may even lead to a decrease in accuracy. Therefore, it is important to carefully consider whether a 3rd order energy perturbation correction is necessary for a given system.

Similar threads

  • Advanced Physics Homework Help
Replies
0
Views
358
  • Advanced Physics Homework Help
Replies
6
Views
391
  • Advanced Physics Homework Help
Replies
13
Views
1K
  • Advanced Physics Homework Help
Replies
2
Views
935
Replies
26
Views
2K
  • Advanced Physics Homework Help
Replies
1
Views
730
  • Advanced Physics Homework Help
Replies
5
Views
1K
  • Advanced Physics Homework Help
Replies
0
Views
293
  • Advanced Physics Homework Help
Replies
1
Views
1K
  • Advanced Physics Homework Help
Replies
7
Views
1K
Back
Top