next up previous contents
Next: Solution of the equations Up: Kohn-Sham equations Previous: Derivative of a real

Kohn-Sham Equations

 

Using what we have just learned about taking derivatives of real functions of complex variables and including the normality constraint of each orbital tex2html_wrap_inline649 with a separate Lagrange multiplier tex2html_wrap_inline811 , the condition for the constrained minimization of (12) is

eqnarray229

We now take this derivative term by term.

The kinetic energy (10) has only one tex2html_wrap_inline651 term in it, so the derivative is just what this term multiplies,

displaymath815

For the electron-nuclear potential energy (3), the only term which depends on tex2html_wrap_inline651 is the charge density, where tex2html_wrap_inline651 multiplies tex2html_wrap_inline821 . The nuclear potential tex2html_wrap_inline673 is unchanged as tex2html_wrap_inline651 varies, so the final term is just

displaymath827

The electron-electron energy has a very similar structure. The only difference is that, here, when we change tex2html_wrap_inline651 , the potential function tex2html_wrap_inline645 also changes because it depends on tex2html_wrap_inline619 . The net effect of the change in tex2html_wrap_inline645 is the same as that of the direct change in tex2html_wrap_inline619 . To see this we note that Poisson's equation tex2html_wrap_inline839 implies also that tex2html_wrap_inline841 . Thus,

displaymath843

where we have moved the tex2html_wrap_inline845 from acting on tex2html_wrap_inline847 to acting on tex2html_wrap_inline849 by integrating by parts twice. Since both terms are equal, we can take just twice the tex2html_wrap_inline851 term,

displaymath853

For the exchange-correlation term, we have already derived in (14) that tex2html_wrap_inline855 . By the chain rule we just need to multiply this by tex2html_wrap_inline857 for the result

displaymath859

Fortunately, tex2html_wrap_inline675 depends only on the nuclear positions and does not change with tex2html_wrap_inline651 , so

displaymath865

And, finally, tex2html_wrap_inline651 only appears once in the constraint term, making the derivative,

displaymath869

Summing all of these contributions, setting the resulting equation to zero, moving the `` tex2html_wrap_inline871 '' term to the right-hand side, and dividing through by tex2html_wrap_inline661 , we get the final result,

displaymath875

Fortunately for us, this is in the form of a very well-known equation for which there are standard techniques. This is in the form of the standard Schrödinger equation,

  equation277

where we define the potential term as

  equation282

and we define tex2html_wrap_inline877 . We interpret the potential tex2html_wrap_inline879 as just the sum of the nuclear potential, the electrostatic potential tex2html_wrap_inline645 created by the electrons, and an extra, ``exchange-correlation'' potential correction, tex2html_wrap_inline883 . Since the Lagrange-multipliers are unknown constants at the start, we may as well think in terms of the tex2html_wrap_inline877 instead, which have the interpretation of the Schrödinger energies for each orbital.


next up previous contents
Next: Solution of the equations Up: Kohn-Sham equations Previous: Derivative of a real

Tomas Arias
Tue Feb 8 12:49:58 EST 2000