14.2 Oxide Tetrahedron Bond Formation
279
closely to the missing row. The Cu
2+ row pairs two Cu
p rows. The (Cu
p
↔ Cu
p )
bridges over the missing row vacancies.
• O
−2 prefers the central position of the M 2 O tetrahedron rather than at an apical site of the tetrahedron. Therefore, O
−2 locates underneath the top layer and
moving close to atom 1, and away from the MR, due to bond contraction.
• The O–Cu–O string is zigzagged by electron lone pairs (Cu
p : O
−2 : Cu
p ) rather
than any other kinds of bonding or antibonding states. The Cu
p
↔ Cu
p antibonding
quadruple is responsible for the “dumbbell” protrusion in the STM image. Missing
row atom is produced by the isolation of this atom from other neighbors during
the bond forming. All neighbors of the MR atom have bonded to the adsorbate and
thus the MR atoms are “evaporated” from the surface.
14.2.6.2 Reaction Dynamics
The present model describes logically beautifully the dynamic process of oxygen
bonding to the Cu(001) surface, in which O
−1 forms first and then turns to O
−2 with
sp-orbital hybridization and lone pair production:
The precursor phase Cu(001) − (2 × 2) − 2O
−1 can be simply described as a
pairing CuO 2 pyramid formation:
O 2 (adsorbate) + 4 Cu(surface) + 2 Cu(substrate)
⇒ 2O
−1
+ Cu
+2
(surface)
(CuO 2 bonding)
+3 Cu
p
(buckled up) + 2 Cu(substrate) (bonding effect);
The MR type Cu(001) − (
√
2 × 2
√
2) R45 − 2O
−2 structure is a consequence of
the pairing CuO 2 pyramid evolves into a novel pairing tetrahedron Cu 3 O 2 :
⇒ 2 O
−2
(hybrid) + Cu
+2
(surface) + 2 Cu
+
(substrate) (Cu 3 O 2 bonding)
+2 Cu
p
(buckled up) + Cu(MR vacancy)
( bonding effect)
As the bonding effect on reconstruction and charge transformation, only the MR
vacancies and the buckled Cu
p are within the scope of experimental observation
while the origin of the phenomena, dynamics of bonding and electron polarizing, is
within the capacity of logic imagination.
14.2.6.3 Surface Bond Network and STM Morphology
Repeatedly packing the complex unit cell forms the bond network of the O–
Cu(001) surface. The STS profiles measured along the O–Cu chain at different sites
from Cu(110) surface verified the electronic configurations of the tetrahedron [40].
According to the Fourier transformation, the performance of atoms and electrons in
279
closely to the missing row. The Cu
2+ row pairs two Cu
p rows. The (Cu
p
↔ Cu
p )
bridges over the missing row vacancies.
• O
−2 prefers the central position of the M 2 O tetrahedron rather than at an apical site of the tetrahedron. Therefore, O
−2 locates underneath the top layer and
moving close to atom 1, and away from the MR, due to bond contraction.
• The O–Cu–O string is zigzagged by electron lone pairs (Cu
p : O
−2 : Cu
p ) rather
than any other kinds of bonding or antibonding states. The Cu
p
↔ Cu
p antibonding
quadruple is responsible for the “dumbbell” protrusion in the STM image. Missing
row atom is produced by the isolation of this atom from other neighbors during
the bond forming. All neighbors of the MR atom have bonded to the adsorbate and
thus the MR atoms are “evaporated” from the surface.
14.2.6.2 Reaction Dynamics
The present model describes logically beautifully the dynamic process of oxygen
bonding to the Cu(001) surface, in which O
−1 forms first and then turns to O
−2 with
sp-orbital hybridization and lone pair production:
The precursor phase Cu(001) − (2 × 2) − 2O
−1 can be simply described as a
pairing CuO 2 pyramid formation:
O 2 (adsorbate) + 4 Cu(surface) + 2 Cu(substrate)
⇒ 2O
−1
+ Cu
+2
(surface)
(CuO 2 bonding)
+3 Cu
p
(buckled up) + 2 Cu(substrate) (bonding effect);
The MR type Cu(001) − (
√
2 × 2
√
2) R45 − 2O
−2 structure is a consequence of
the pairing CuO 2 pyramid evolves into a novel pairing tetrahedron Cu 3 O 2 :
⇒ 2 O
−2
(hybrid) + Cu
+2
(surface) + 2 Cu
+
(substrate) (Cu 3 O 2 bonding)
+2 Cu
p
(buckled up) + Cu(MR vacancy)
( bonding effect)
As the bonding effect on reconstruction and charge transformation, only the MR
vacancies and the buckled Cu
p are within the scope of experimental observation
while the origin of the phenomena, dynamics of bonding and electron polarizing, is
within the capacity of logic imagination.
14.2.6.3 Surface Bond Network and STM Morphology
Repeatedly packing the complex unit cell forms the bond network of the O–
Cu(001) surface. The STS profiles measured along the O–Cu chain at different sites
from Cu(110) surface verified the electronic configurations of the tetrahedron [40].
According to the Fourier transformation, the performance of atoms and electrons in