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Charge degeneracy for a ThomasFermi hydrogen molecule:
Boundunbound transition
Jo ao B. Diniz
a,c
, Andr e L.A. Penna
a,c,
, S ergio L. Garavelli
b,c
, Fernando A. Oliveira
a,c
a
Instituto de Fsica - Universidade de Brasilia, CP 04455, 70919-970 Brasilia DF, Brazil
b
Departamento de Fsica - Universidade Cat olica de Brasilia, CP 04455, 70919-970 Brasilia DF, Brazil
c
International Center for Condensed Matter Physics, CP 04455, 70919-970 Brasilia DF, Brazil
Received 3 December 2007; received in revised form 21 January 2008; accepted 23 January 2008 by F. De la Cruz
Available online 6 February 2008
Abstract
We study the relationship between quantum screening effects and charge symmetry in the hydrogen molecule. In this model, the charge
symmetry of the molecule is broken in the presence of the ThomasFermi potential exp(qr)/r. We argue that screening acts as an external eld
that promotes charge degeneracy in the system. In the presence of screening (q = 0), the charge symmetry of the H
+
2
molecule is broken and
thus the effective nuclear charge splits into two, (, ), where is the dual charge. The effective nuclear charge is then related to the
binding energy of the electron, while the dual charge is responsible for the screening effect in the wavefunction. Naturally, both the energy and
the wavefunction are modied by this charge degeneracy. We obtain an analytical formulation for the molecular energy with a charge degeneracy
effect. To test the efciency of our model, we analyze the behavior of the molecules energy as a function of the ThomasFermi parameter q and
calculate the critical parameter q
k+1
( p) =
2
p
2
2E
k+1
_
V( p
p)
k
( p
) d
3
p
, (2)
where
k
( p) and
V( p) are the Fourier transforms of the
wavefunction and potential equation (1), respectively; k =
1, 2, . . . is the order of the iteration. Note that the potential
k+1
( p) is iterated
for each k. For the screened hydrogen atom, it is reasonable
to suppose that the energy E
k
is associated with an effective
nuclear charge
k
viewed by the electron, which assumes the
form
2
k
= 2E
k
. (3)
We can start with the wavefunction of the ground state in
the momentum space,
1
( p) = a
1
/( p
2
+
2
1
)
2
, which is the
solution for the unscreened hydrogen atom (q = 0), where a
1
is a constant. After a few iterations, we then obtain an analytical
expression for Eq. (2) as
k+1
( p) =
a
k
( p
2
+
2
k
)( p
2
+
2
k
)
, (4)
where a
k
is a constant. We introduce a newparameter,
k
, which
is related to the nuclear charge of the system,
k
, according to
2
k+1
= (
k
+ q)(
k
+ q). (5)
Here we note a quantitative gain: we start out from an iterative
process with complicated integrals and end up with the simple
algebraic recurrence relationships in Eqs. (4) and (5). This
means that after many iterations the k index can be dropped.
The inverse Fourier transform of Eq. (4) yields the SWF of the
ground state, namely
(r) =
e
r
e
r
( )r
= e
r
g(r), (6)
where = is the screening parameter of the screening
factor g(x) = (1 e
x
)/x. Note that screening acts as
an external eld that breaks down the charge symmetry and
creates the order parameter . Note that the parameter
becomes a new charge in theory and provides screening in
the wavefunction. In the absence of screening (q = 0), we can
conjecture that the charges and are symmetrical, which
might correspond to charge degeneracy in the system. We
believe that charge symmetry is important for understanding the
quantum screening effects in atomic and molecular structures.
In the present study, we investigate the relationship between
quantum screening effects and charge degeneracy in the
screened H
+
2
molecule. To understand the screening effect,
we argue that each hydrogen atom of the molecule H
+
2
has
a hidden charge degeneracy due to the Coulomb potential,
which establishes a charge symmetry in the molecular structure.
This motivated us to search for charge degeneracy (or charge
symmetry breaking) for the ThomasFermi molecule. This
means that in the presence of screening (q = 0), the effective
nuclear charge is degenerated (, ), giving rise to a
dual charge
1
responsible for screening in the wavefunction
of the system. Our main goal is to investigate novel aspects
due to the charge degeneracy of this molecular system. In this
communication, we show how charge degeneracy affects the
molecular energy and the effective nuclear charge of the system.
The boundunbound transition is analyzed, and we obtain its
critical parameter q
.
Finally, we discuss a super-freezing screening phenomenon
observed for a region where (q) 0 for q = 0 in the
ThomasFermi hydrogen molecule.
2. Charge degeneracy
Symmetry plays a fundamental role in describing important
natural phenomena in physics, which prompted us to explore
how the charge symmetry of the unscreened hydrogen molecule
is related to the quantum screening phenomenon. We start
with the hydrogen atom in the absence of screening (q = 0),
whose charge interaction is then mediated by a Coulomb-
type potential. In this case, charge symmetry dictates that the
electron sees only a well-dened and symmetrical effective
nuclear charge for the whole system. In a Coulomb potential,
the hydrogen atom exhibits a hidden charge degeneracy that
establishes a charge symmetry for the electron in any quantum
state. On the other hand, in the presence of a ThomasFermi
potential, there is a nuclear charge degeneracy manifested that
gives rise to charge symmetry breaking in the atomic system.
This suggests that the ThomasFermi parameter q acts as an
external eld in breaking down the charge symmetry of the
atom to create a quantum screening phenomenon. The charge
degeneracy then promotes the splitting of the nuclear charge
into two charges: an effective nuclear charge and a dual
charge , which modify the energy and wavefunction of the
1
The dual term refers to degeneracy (, ), which is a pair (or dual).
We then denote as the dual charge.
J.B. Diniz et al. / Solid State Communications 146 (2008) 169174 171
electron. Hence, charge symmetry is recovered when =
as q = 0, i.e., both the charges and are symmetrically
indistinguishable, or not degenerate. In this case, the electron
sees only the nuclear charge of the molecule. In fact,
it elucidates the hidden charge degeneracy in the hydrogen
molecule. This symmetry can be seen for the hydrogen atom
by taking the limit into Eq. (6), where we recover the
unscreened wavefunction (UWF) for the ground state. On the
other hand, for q = 0, the model exhibits charge degeneracy,
which means that = , and so the electron sees two
effective charges and with different numerical values. In
this sense, the effective nuclear charge is directly related to
the binding energy of the molecule, whereas the dual charge
is responsible for the screening in the wavefunction by
changing the binding energy of the system.
In this model, we assume that when q increases the nuclear
charge degenerates and and depart from each other. The
charge degeneracy allows us to dene the order parameter,
= , which can be called the screening parameter
of the wavefunction. Note that this parameter depends on the
dual charge , as well as on the effective nuclear charge .
Thus, the screening parameter depends on the existence of
charge degeneracy in the system. If = 0, charge symmetry is
recovered ( = ) in the model (no screening).
We are now ready to study the ThomasFermi H
+
2
molecule with a charge degeneracy effect. We xed the
protons at the positions (0, 0, R/2) and (0, 0, +R/2), while r
denotes the electron position. In this framework, the molecular
wavefunction is given by the combination, (r) = (|r +
R
2
|) + (|r
R
2
|), where is the screened atomic function,
dened by Eq. (6), and R is the distance between the ions. In
this case, V(|r +
R
2
|) and V(|r
R
2
|) are the electronproton
interactions, while V(|R|) represents the protonproton
interaction, according to the denition of Eq. (1). Since we
consider the protons xed, i.e. no vibrations, we have no extra
contributions for the dielectric constant. As a consequence, the
protonproton interaction is only modulated by the electronic
screening, in the same way as the electronproton interaction.
We begin by writing the Hamiltonian for a screened
molecular system by considering the ThomasFermi potential
equation (1)
H =
2
2m
+ V
_
r +
R
2
_
+ V
_
r
R
2
_
V(|R|). (7)
We note that both Hamiltonian and wavefunction are invariant
to the transformation r r. We then start out with the
Hamiltonian operator
H to calculate the functional energy E
of the molecular system
E =
(r)|
H|(r)
(r)|(r)
=
(|r+
R
2
|)|
H|(|r+
R
2
|)+(|r+
R
2
|)|
H|(|r
R
2
|)
(|r+
R
2
|)|(|r+
R
2
|)+(|r+
R
2
|)|(|r
R
2
|)
. (8)
Here we shall use atomic units. From Eq. (8) we obtain the
energy
E = K +U +
e
q R
R
, (9)
where the kinetic energy and the electronic contribution to
the potential energy, which can be analytically computed, are
respectively given by
K =
1
N
_
e
R
2
_
4
R
+
2
R
_
e
R
2
_
4
R
+ +
2
R
_
+
2
2
_
,
U =
N
_
2A(q)
[A(q) A(q)]e
q R
q R
+ B(q) + B(q) + C(, ) + C(, )
_
,
where = + , N is the normalization constant
N =
2
+ e
R
_
4
R
+
_
+ e
R
_
4
R
+
_
,
and
A(q) = ln
_
(2 + q)(2 + q)
( + q)
2
_
,
B(q) =
e
q R
q R
{Ei ((2 + q)R)
+ Ei ((2 + q)R) 2Ei (( + q)R)},
C(, ) =
2e
R
R
_
ln
_
(2 + q)( + q)
(2 + + q)q
_
+ Ei (( + q)R) Ei (q R)
_
2e
R
R
{Ei ((2 + q)R) Ei (( + q)R)}.
Here, Ei (x) is the exponential integral function. Note that
calculation of the energy, Eq. (9), results in a lengthy but
analytical equation. Using iterative and variational procedures,
we now analyze the behavior of the energy (9) and of
parameters (effective nuclear charge), (dual charge), and
(screening parameter).
3. Numerical results
We dene an iterative process using Eqs. (3) and (9). This
method allows us to obtain the energy and the parameters
and as functions of q. Furthermore, we compare the
results obtained from the iterative method with those from the
variational procedure, which consists of minimizing Eq. (9) in
relation to the parameters and .
In Fig. 1, we present the energy E(R) as a function of the
inter-atomic distance R for (a)(c) q = 0. Curve (a) shows
the iterative process, which has a minimum at R
eq
= 2.330
and binding energy of E
a
= 0.5761. Curve (b) shows the
results of the variational process for the UWF ( = 0), which
has a minimum at R
eq
= 2.033 and binding energy of E
b
=
0.5865, in good agreement with Coulson value E
coulson
=
0.5648 [46]. Curve (c) shows the variational process for SWF
172 J.B. Diniz et al. / Solid State Communications 146 (2008) 169174
Fig. 1. Energy as a function of inter-protonic distance R (atomic units). Curves
(a)(c) for q = 0. Curves (d)(f) for q = 0.5. Curves (a), (e): iterative process;
curves (b), (d): variational process for the UWF; curves (c), (f): variational
process.
for q = 0. It should be noted that the curves (c) and (b)
are identical (same values for R
eq
and E
c
). As expected, the
variational result is better than the iterative result. However,
we should bear in mind that the energy used in the variational
process (Eq. (9)) was obtained using the iterative process. The
minimization process yields better values of and than the
iterative process, which may be improved to provide a new
wavefunction and energy. Despite its limitation, the iterative
process is better than the variational procedure for the UWF as
q increases. For curves (d)(f), q = 0.5. Again the variational
energy in curve (f) is lower than the UWF, represented by curve
(e) and the iterative result shown in curve (d).
In Fig. 2, we plot the binding energy E
b
as a function of
the ThomasFermi parameter q. Curve (a) is for the variational
process, curve (b), for the iterative process while curve (c) is
for the variational process for the unscreened function ( = 0).
Note that for very small q the variational processes with the
SWF and UWF yield better results than the iterative process for
the screened function. For values of q > 0.08, both iterative
and variational process with the screened functions yield better
results than the UWF, which shows the importance of screening
in the wavefunction, even for small q. The critical value q
for
the existence of the bound state, i.e., E(q
) = 0, is q
= 1.3964
for the variational procedure, q
= 1.9176 and
=
2.2108, respectively. We recognize that the variational critical
parameters q
and
eq
= 3.9713 at
q
eq
= 4.3905 at q
= 1.3641; curve
Fig. 2. Binding energy as a function of the ThomasFermi parameter q (atomic
units). Curve (a): variational process; curve (b): iterative process; curve (c):
variational process for the UWF.
Fig. 3. Inter-protonic distance R as a function of the ThomasFermi parameter
q (atomic units). Curve (a): variational process; curve (b): iterative process;
curve (c): variational process for the UWF.
(c) R
eq
= 4.3117 at q
= 1.1906. For a
given q a better result means a large binding energy and a small
radius. However when we compare curves (b) and (c) we notice
that in the region 0.08 < q < 0.46, R
c
< R
b
, nevertheless
E
b
< E
c
. This is due to the fact that the set of parameters
, , R are enough to yield good energy, and not only R. In
any circumstance however curve (a) yields better E and R
eq
as expected. The nite value of our R
eq
is a balance between
its fast growth at the boundunbound transition and the system
aversion to the atomic limit
R R
eq
and E
H
> 0 > E
H
+
2
. (10)
In Fig. 4, we plot the charge and the screening parameter
as functions of q. This plot is critical in elucidating the
difference between the methods and the subtle physics within.
Curves (a) and (b) represent for the iterative and variational
procedures, respectively. Note that in both curves is an
increasing function of q. However, for the iterative method
the increase is continuous, whereas for the (more precise)
variational method it starts at a small value and the screening
becomes effective only for q 0.6 or 1.0. It is interesting
J.B. Diniz et al. / Solid State Communications 146 (2008) 169174 173
Fig. 4. Effective nuclear charge and screening parameter as functions of
the ThomasFermi parameter q (atomic units). (a), (b) Curves for obtained
using the iterative and variational processes, respectively. (c)(e) Curves for
obtained using the variational process for the UWF, the variational process and
the iterative process, respectively.
that only for charges smaller than the bare atomic charge does
the screening parameter become non-null for the variational
method. The smoothness of curve (a) is once again a limitation
of the recurrence relation given by Eqs. (3) and (5). Curves
(c)(e) display for the unscreened function and the variational
and the iterative methods, respectively. In curve (c), decreases
with q, with a nite critical