1.
Interaction between orbitals
The manuscript “Enhancing planar anisotropy in a bulk Fe4N system with doping (W/Ta):
First principle calculation” reported results of first principles calculations on magnetic
properties of γ′-Fe4N, Fe3NTW, Fe3NTa systems.
1. γ′-Fe4N systems where extensively studied and concluded PBE+U with U=0.4eV was
identified as most accurate to experimental results. PBE method used for this slightly
underestimates magnetic moments of Fe.
2. Temperature dependent calculations predicted curie temperature of 630K for γ′-Fe4N
which vastly underestimates experimental curie temperature of 767±10K.
Temperature dependent magnetization curve in this work shows constant sharp
decline in magnetization, which is contrary to previous experimental works in
temperature dependent properties in γ′-Fe4N where there are ce.
3. With doping magnetocrystalline anisotropy did improve up to 0.46MJ/m-3 but at a
cost of saturation magnetization, decreasing it from 2.58T to 1.55T. This result is
equivalent to hardness factor of 0.46, which is vastly inferior to currently widely used
ferrites.
In case of graphene we only consider s and p orbitals and those orbitals interact with each
other to create interatomic potential. When two orbitals from different atoms interact with
each other π bond is created. On the other hand when two orbitals overlap σ bond is created.
Depending on the state those bonds can be either bonding or anti-bonding if orbital is fully
filled with 2 electrons. If the orbital has only single electron it is called “non-bonding orbital”
which is neither bonding nor anti-bonding. In a case of carbon, it has 6 electrons and 4 of
which are valence electrons in s, px, py and pz orbitals and specifically in case of graphene
there are only σ and π bonds. Specifically σ bond between two s orbitals, σ bond between s
and p orbital, σ bond between two p orbitals, and lastly π bond between two p orbitals (figure
2).
https://www.differencebetween.com/difference-between-antibonding-and-
nonbonding/
AH Castro Neto, F
Guinea, NMR Peres, Kostya S Novoselov, and Andre K Geim. The electronic properties of
graphene. Reviews of modern physics, 81(1):109, 2009.
2. Hamiltonian for graphene
If we denote 2 atoms in a unit cell of graphene as A and B, according to a Bloch theorem and
tight binding model general Hamiltonian can be written in a following way:
ψ ( r )=∑ ψ A ( R A ) ϕ ( r−R A ) + ∑ ψ B ( R B ) ϕ ( r−R B )
RA RB
Now before constructing Hamiltonian matrix let us consider following:
1. For π band, interaction between pz orbital of one atom and s, px, py orbital of the
other atom is 0 (This assumption was made to simplify the matrix, I am not sure if it
is correct)
2. For σ band, s orbital of an atoms will not have interaction with p orbitals of same
charge.
3. Let us denote Vi as intra-atomic hybridization potential between s and p orbitals with
different charge.
4. Let us denote Vσ as tight binding parameter between two electrons with different
charge in same orbital.
5. Let us denote Eσ as tight binding parameter between two electrons with same charge
in s, px, and py orbital.
6. Let us denote Eπ as tight binding parameter between two electrons with same charge
in pz orbital.
Considering each carbon atom has 3 nearest neighbors with following vectors as vector
connecting the atom to the nearest neighbors a 1 , a2 , a3.
(
+ ¿¿ −¿ ¿ +¿¿ −¿ ¿ +¿¿ −¿ ¿ +¿¿ −¿ ¿ +¿¿ ik a1
s s px px p y py pz pz s Eσ V σ e Vi 0 Vi 0 0 0 ik a2
−¿¿ −ik a1
0¿ E σ ¿V σ e ¿V i ¿0¿
s Vσ e Eσ 0 Vi 0 Vi 0 ¿ ¿
Here A is interaction between two pz orbitals of different charge. Let us delve deeper into A.
If we denote potential between two pz orbitals of different charge as V π then
ik a ik a ik a ¿ −ik a −ik a −ik a
A=V π (e +e + e ) and A =V π ( e
1 2 3
+e +e
1
) 2 3
Task 1: Only consider pz orbital
For pz orbital only case we should solve the problem on 2x2 part at the bottom right of the
matrix. In that case energy can be found as:
¿
E ( k )=¿ Eπ ∨±∨A A ∨¿
and considering the fact that E π and V π are real numbers, we get:
−ik a1 −ik a2 −ik a3 ik a1 ik a2 ik a3
E ( k )=E π ±V π ∨( e +e +e )(e +e +e )∨¿
and in case of a graphene a 1=a0 0 ,
1
√3( ; a 2=a0
−1
2) ,−
1
2 √3 ( 1
;a 3=a 0 ,−
2
1
2 √3
where a 0is ) ( )
distance between two carbon atoms in graphene unit cell, thus we get:
E ( k )=E π ±V π ¿
