Monday, September 9, 2013

qmchem01 Born-Oppenheimer approximation Relativistic effects

In materials simulations the external potential Vext is usually the




interaction of the electrons with the nuclei. Thus:
( )
1
N

ext
Z

V
a
a

a = a





=

r

r R
The separation of electron and nuclear degrees of freedom is valid

under the Born-Oppenheimer approximation. Relativistic effects are neglected
 




neglected.

The external potential and the number of electrons therefore

completely determine the Hamiltonian H.




We assume for simplicity a nondegenerate ground state. Then the

wave function must be anti-symmetric under exchange




of its arguments (Pauli-principle) and we assume
is normalized.

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氫原子核對電子Born-Oppenheimer approximation  Relativistic effects

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