THE JOURNAL OF CHEMICAL PHYSICS 125, 114108 2006

Two-electron distribution functions and short-range electron correlations

of atoms and molecules by first principles T-matrix calculations
Yoshifumi Noguchi, Soh Ishii, and Kaoru Ohnoa
Department of Physics, Graduate School of Engineering, Yokohama National University, 79-5 Tokiwadai,
Hodogaya, Yokohama 240-8501, Japan
Received 2 May 2006; accepted 10 August 2006; published online 21 September 2006

The accurate first principles description of the correlations between electrons has been a topic of
interest in molecular physics. We have reported in our previous paper J. Chem. Phys. 123, 144112
2005 that the T matrix, which is the ladder diagrams up to the infinite order, can accurately
represent the short-range electron correlations while calculating the double ionization energy spectra
of atoms and molecules. In this paper, we calculate the two-electron distribution functions of real
systems Ar, CO, CO2, and C2H2 from the eigenvalue equation associated with the Bethe-Salpeter
equation for the T matrix by beginning with the local density approximation of the density
functional theory and the GW approximation. We found that when the interelectron distance is very
small, the Coulomb hole appears between antiparallel spin electrons due to the short-range repulsive
Coulomb interaction. The resulting two-electron distribution functions clearly show the Coulomb
hole. 2006 American Institute of Physics. DOI: 10.1063/1.2348879

I. INTRODUCTION ceeded in calculating the Coulomb hole in an electron gas by

evaluating the particle-particle ladder diagrams.
Two-electron distribution functions provide significant
information on the electron correlations between two par- The aim of this paper is to elucidate the effect of the
ticles. When the interelectron distance is very small, there short-range electron correlations between two particles by
are two kinds of electron avoidance known as the exchange explicitly calculating the two-electron distribution functions
hole for parallel spins due to Paulis exclusion principle and of real systems, for the first time, from the first principles
the Coulomb hole for antiparallel spins due to the short- using Greens function method. For this purpose, we intro-
range repulsive Coulomb interaction. If the Coulomb hole is duce a two-particle Greens function and calculate it in the
described from the first principles, the short-range correla- T-matrix theory that describes the multiple scatterings be-
tions between electrons can be treated accurately. However, tween two particles. Then, we solve the Bethe-Salpeter equa-
there has been no such theoretical attempt so far because tion BSE for the T matrix via an eigenvalue problem and
two-particle wave functions are not the simple product of compose the two-electron distribution functions from the
two one-particle wave functions but require a two-particle eigenfunctions see next section.
picture that can effectively include the electron repulsive- By calculating the double ionization energy DIE spec-
ness. tra in which the short-range repulsive Coulomb interaction
In an electron gas, a number of calculations of the radial plays an important role, we have already demonstrated in our
pair distribution function describing the Coulomb hole have previous paper5 that the T matrix describes the strong short-
already been performed, and these have indicated the impor-
range electron correlations in atoms and molecules. The cal-
tance of the treatment of short-range electron correlations.
culated DIE spectra are in good agreement with the corre-
For example, the Hartree-Fock approximation fails in evalu-
sponding experimental values. The short-range electron
ating the Coulomb hole, that is, the radial pair distribution
function for antiparallel spin electrons is constant over the correlations cannot be simply expressed by an expectation
entire region from the long-range to the short-range limit value of the bare Coulomb interaction 1 / r. Furthermore, the
because of the lack of electron correlations. The random multiple scatterings between two electrons are very impor-
phase approximation RPA also fails to evaluate the Cou- tant when the interelectron distance is very small; in the case
lomb hole. The RPA fails at low densities, i.e., the radial pair of the 1,3,5-trithia-2,4,6-triazapentalenyl TTTA, the effect
distribution function for antiparallel spin electrons becomes of the short-range interaction reduces the bare Coulomb in-
negative in the short-range limit.1 However, Carbotte2 found teraction by a few eV.6
that the negativeness of the antiparallel spin radial pair dis- In the present paper, we calculate the two-electron dis-
tribution function within the RPA can be removed by taking tribution functions of Ar, CO, CO2, and C2H2 by means of
into account the multiple scatterings between electrons in the first principles T-matrix theory. Deriving the two-electron
terms of ladder diagrams up to the infinite order referred to distribution functions and comparing them with the one-
as the T matrix; later Hede and Carbotte3 and Yasuhara4 suc- electron distribution functions, we visually describe the ef-
fect of short-range electron correlations in terms of the Cou-
a
Electronic mail: ohno@ynu.ac.jp lomb hole. Moreover, we discuss the relationship between

0021-9606/2006/12511/114108/6/$23.00 125, 114108-1 2006 American Institute of Physics

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114108-2 Noguchi, Ishii, and Ohno J. Chem. Phys. 125, 114108 2006

the dependence in K is eliminated by subtracting

in Eq. 4 and thus H is independent of . Then, we
solve the eigenvalue problem as follows:

HA = A. 5

FIG. 1. Schematic representation of the BSE for the T matrix square. The From the eigenvalues and eigenfunctions A, one can
dotted lines represent the bare Coulomb interaction U. The solid lines with construct the T matrix associated with both the hole-hole and
an arrow represent the one-particle Greens function G1. electron-electron two-particle Greens functions. The eigen-
values , which are the poles of the T matrix, directly pro-
the Coulomb hole and short-range electron correlations in vide the DIE spectra. A represents the coefficients in the
detail. The present paper should be regarded as part II of our double expansion using the LDA one-particle wave func-
previous paper.5 tions for the spatial part of the Bethe-Salpeter amplitude
two-particle wave function,
r,r = A*rr, 6
II. METHODOLOGY

First, we begin with local density approximation LDA which is either symmetric or antisymmetric with respect to
of density functional theory and introduce the GW approxi- the interchange of the particles. The absolute square of Eq.
mation GWA perturbatively.7,8 In the present calculation, 6 represents the two-electron distribution function for a
we employ an all-electron mixed basis approach in which the given two-particle state .
wave functions are expanded in a linear combination of both For the calculation with regard to the CO2 molecule, we
atomic orbitals AOs and plane waves PWs.9,10 This ap- employ an fcc supercell with a cubic edge of 30 a.u. and the
proach can describe all the states from the core states to free corresponding PW cutoff energy is 25.1 Ry. In the calcula-
electron states efficiently. In order to take into account the tion of x and U, the cutoff energy of the G vectors is
short-range Coulomb interactions, we express the two- 46.0 Ry. For the calculation of c, the cutoff energy of G
particle Greens function G2 in terms of the T matrix as G is 19.5 Ry and 5000 levels 462 eV are needed to
follows: achieve a good convergence of the results. The details of the

d3d4T1,23,4G13,3G14,4
calculation for other atoms and molecules are the same as in
Ref. 5.

= U1,2G21,23,4, 1
III. RESULTS AND DISCUSSION
where U1 , 2 is the bare Coulomb interaction and G1 is the
Our approach, through which the eigenvalue problem
one-particle Greens function. The T matrix satisfies the fol-
Eq. 5 is solved, can be used to calculate the two-electron
lowing BSE:11
distribution functions from Eq. 6. The Bethe-Salpeter am-
T1,23,4 = U1,21 32 4 plitude two-particle wave function r , r is in a double

space with coordinates r and r that refer to the positions of
+ iU1,2 d1d2K1,21,2 electrons. If the eigenfunctions A are replaced by ,
r , r will not include any electron correlation between
T1,23,4, 2 the two particles, i.e., we have r , r without the interac-
tion. To discuss r , r with the interaction, we fix the
where K is the noninteracting two-particle Greens function position of one electron at r and consider the distribution of
K1 , 2 1 , 2 = iG11 , 1G12 , 2. Here, we introduce a the other electron as the function of r. In this section, the
shorthand notation r1 , t1 1. Diagrammatically, the T ma- effect of the short-range electron correlation and the Cou-
trix is represented in Fig. 1. This equation is sandwiched by lomb hole is discussed in detail.
the LDA one-particle wave functions and is reduced to a
matrix equation.5 K = K is then given by
A. Argon
occocc empemp
K = + , 3 First, we solve Eq. 5 for an isolated argon atom. Figure
E E i E E + i
2 shows the absolute square of the two-particle wave func-
where E and E denote the one-particle energies determined tions r , r2 without dotted lines and with solid lines
by the GWA and occ emp is unity if is occupied empty the interaction. This two-particle state corresponds to the 3p
and zero otherwise. We define the two-particle Hamiltonian valence level in the viewpoint of one-particle picture. Here,
H as an atomic nucleus is the origin of the horizontal axis, and an

H f
K

U f , 4
electron is fixed at the position r = a, 2, b 9, c 19,
and d 44 on the horizontal axis. The scale of the horizon-
tal axis is indicated in Fig. 2a. The dotted lines are identical
where we defined f as f = occocc + empemp. Note that to the absolute square of the one-particle wave functions

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114108-3 Two-electron distribution functions J. Chem. Phys. 125, 114108 2006

FIG. 2. The two-electron distribution functions without dotted lines and with solid lines interaction of Ar. Here, an atomic nucleus is the origin of the
horizontal axis given in mesh unit 1 mesh is about 0.08 and one electron is assumed to fix at r = 2 a, 9 b, 19 c, and 44 d on the horizontal
axis, respectively. The scale of the horizontal axis is indicated in a.

r2 = 3p, which do not include the electron correla- breaking of the point symmetry. Another remarkable point is
tions between two particles and have a point symmetry at the that electron depletion appears only in the negative region of
origin of the horizontal axis and no amplitude at the origin. the horizontal axis, while the electron distribution in the
Needless to say, the dotted lines do not change according to positive region is slightly higher than that around the dotted
the position of the fixed electron. On the other hand, the solid line. Because the repulsive Coulomb interaction from the
lines include the effect of the short-range electron correla- fixed electron is sufficiently screened by the other electron
tions i.e., multiple scattering via the T-matrix theory. Be-
with the same p-type character or the electrons with the
cause there is a strong repulsive Coulomb interaction from
s-type character at the origin, there is no decrease in the
the fixed electron, the shapes of the four solid lines in Fig. 2
electron distribution in the positive region. When an electron
are different from those of the dotted lines. The remarkable
common characteristics of the solid lines in Figs. 2a2d is fixed further away from the atomic nucleus, the shapes of
are the breaking of the point symmetry, and a finite ampli- the solid and dotted lines resemble each other see Figs. 2c
tude at the origin, although this state is nevertheless the 3p and 2d. In particular, the difference between the solid and
level. The repulsive Coulomb interactions have a stronger dotted lines in Fig. 2d is small.
effect when the fixed electron is closer to the atomic nucleus; The two-electron distribution function shown in Figs.
therefore, the change in shape from the dotted lines is the 2a2d corresponds to the state characterized as 1, which
largest in Fig. 2a and the smallest in Fig. 2d among Figs. has a DIE of = 47.8 eV this value is already given in Ref.
2a2d. In the case of Fig. 2a, one electron is fixed at the 5. Then, the actual Coulomb interaction given by Ref. 12
position r = 2 where the dotted lines have the maximum + E + E = = 3p, which acts between two particles
amplitude, and an s-type character newly appears to screen with antiparallel spin in the same 3p level and includes the
the atomic nucleus in addition to the electrons that have al-
short-range correlations i.e., multiple scatterings via the
ready distributed around the atomic nucleus. Moreover, there
T-matrix theory, is estimated to be about 16.0 eV. This value
is clearly a change in the electron population over the broad
region not only in the negative region but also the positive is slightly different as compared to the simple expectation
region of the horizontal axis except at the position of the value of the bare Coulomb interaction U=16.4 eV.
atomic nucleus. Next, we fix one electron at the outer posi- This decrease of about 0.4 eV by the multiple scatterings is
tion r = 9 on the horizontal axis. The solid line in Fig. rather small compared to the other molecules discussed be-
2b is closer to the dotted line in contrast to the case of Fig. low, but it clearly indicates the effect of the short-range cor-
2a, although there still remains the s-type character and the relations, i.e., the Coulomb hole.

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114108-4 Noguchi, Ishii, and Ohno J. Chem. Phys. 125, 114108 2006

FIG. 3. The two-electron distribution functions of CO molecule a without

and b and c with Coulomb interaction. The contour lines are plotted on
the molecular plane. Two closed circles are a carbon atom and an oxygen
atom from up to down. In b and c, one electron is fixed at the point FIG. 4. The two-electron distribution functions of CO2 molecule without a
marked by the cross. The contour lines in b and c clearly indicate the and with b interaction. The center closed circle is a carbon atom and the
Coulomb hole around the cross. others are oxygen atoms. In b, the one electron is fixed at the point marked
by the cross.
B. CO
der diagrams up to the infinite order correctly include the
We performed a similar calculation for the CO molecule. effect of the multiple scattering between two particles.
Figure 3 shows the calculated two-electron distribution func-
tions a without and with b, and c the Coulomb inter-
C. CO2
action in the highest occupied molecular orbital HOMO
level. Contour lines are plotted on a plane including the mo- We plot the two-electron distribution functions of the
lecular axis, and the two closed circles present a carbon atom CO2 molecule in the HOMO level on the molecular plane as
and an oxygen atom from up to down, respectively. One shown in Fig. 4. The closed circle at the center in Fig. 4 is a
electron is fixed at both the point marked by the cross Fig. carbon atom and the others are oxygen atoms. The two-
3b near the oxygen atom and that Fig. 3c near the electron distribution function without the interaction is
carbon atom. In Figs. 3b and 3c, the electron distribution shown in Fig. 4a. It has two mirror symmetries, up and
around the cross is considerably decreased as compared to down symmetries and right and left symmetries. Further-
Fig. 3a due to the strong short-range Coulomb interaction more, the mirror axes are nodes with no amplitude. On the
from the fixed electron, indicating the Coulomb hole. An- other hand, the two-electron distribution function with the
other remarkable feature in Figs. 3b and 3c is that the interaction, which has one electron fixed at the point marked
Coulomb hole moves according to the position in which one by the cross, is represented in Fig. 4b. The node between
electron is fixed. In particular, a considerable enhancement in the up and down sides disappears in Fig. 4b due to the
the electron distribution at the opposite side of the fixed elec- effect of the fixed electron; the symmetry such as that in Fig.
tron is observed in Fig. 3c. 4a is not observed. We see again the remarkable effect of
Comparing Figs. 3a and 3b, we find a slight shift in short-range electron correlations as the Coulomb hole in Fig.
the electron distribution from the oxygen atom to the carbon 4b.
atom and an enhancement of the electron distribution around The two-electron distribution function discussed here is
the carbon atom, and identify the Coulomb hole around the characterized as 1. The corresponding DIE is calculated
cross near the oxygen atom. Similarly, Fig. 3c has a con- to be about 38.4 eV and is in good agreement with the ex-
siderable shift in the electron distribution from the carbon perimental value 38.5 eV.13 We also estimate that the ac-
atom to the oxygen atom and indicates the Coulomb hole tual Coulomb interaction between two particles in the
around the cross near the carbon atom. The electron at the HOMO level is 11.4 eV and the corresponding bare Cou-
HOMO level of the CO molecule originally has higher dis- lomb interaction is 13.5 eV. Therefore, the multiple scatter-
tributions in the carbon atom side than the oxygen atom side. ings between electrons reduce the repulsive Coulomb inter-
Therefore, a shift in the electron distribution from the oxy- action by 1.9 eV, thus reflecting the effect of the Coulomb
gen atom to the carbon atom is not significant even if one hole.
electron is fixed near the oxygen atom. These results are To discuss the short-range electron correlations in
physically reasonable and correctly show the effect of the greater detail, we now present the DIE spectra of the CO2
strong short-range electron correlations. molecule. Table I shows the calculated DIEs and the corre-
Here, using the T-matrix theory, we estimate the actual sponding experiments.13,14 The DIEs shown in the column of
Coulomb interaction between the electrons + E + E to be GWA 2 are E E obtained from the evaluation of the
about 13.0 eV, while the corresponding bare Coulomb inter- noninteracting two-particle Greens function K, namely,
action U = = HOMO is about 15.0 eV. This differ- twice the ionization potential within the GWA. The ioniza-
ence of 2.0 eV is due to the Coulomb hole. To discuss the tion potential within the GWA is evaluated to be about
Coulomb hole, the short-range electron correlations have to 13.7 eV and is in good agreement with that of the experi-
be accurately treated as in the present study. The short-range ment 13.8 eV.15 The HOMO level of CO2 is the orbital
electron correlations obtained from the evaluation of the lad- and is twofold degenerated. When two electrons are removed

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114108-5 Two-electron distribution functions J. Chem. Phys. 125, 114108 2006

TABLE I. The DIEs of CO2 in eV. T matrix and U denote the results
obtained by the T matrix and the matrix element of the bare Coulomb
interaction carrying the largest contribution to the double ionization energy,
respectively. The available photoelectron-photoelectron coincidence spec-
troscopy PEPECO experimental data are given for comparison.

Calc.
Expt.
GWA 2 T matrix U PEPECO
3
27.37 37.95 13.41 37.35a, 37.65 0.3b
1
27.37 38.44 13.46 38.52a
1
27.37 38.75 13.41 39.30a
3
31.89 41.10 12.78 41.43a
1
31.89 41.52 12.78 42.30a
a
Reference 13.
b
Reference 14.
FIG. 5. The two-electron distribution functions a without and b with
interaction of C2H2 molecule. The contour lines are plotted on the molecular
from the HOMO level, the DIEs split into three states, plane. From top to bottom, the four closed circles denote hydrogen, carbon,
carbon, and hydrogen atoms, respectively. In b, one electron is fixed at the
namely, 3, 1, and 1, according to the two-hole states.
point marked by the cross.
Nevertheless, GWA 2 is identical in and , and a differ-
ence in the spin symmetries of 3 and 1 can be ignored
because they do not include the effect of the repulsive Cou- difference with the bare Coulomb interaction U is about
lomb interaction. In every state given in Table I, the differ- 4.0 eV. This large effect of the short-range interaction, which
ences between GWA 2 and the experiments are more than reduces the bare Coulomb interaction by about 4.0 eV,
10 eV. On the other hand, the T matrix, which denotes the clearly indicates the existence of the Coulomb hole.
values evaluated with the T-matrix theory, considerably im-
proves GWA 2 and is in good agreement with that of the IV. SUMMARY
experiments. The difference with the experiments is about In summary, we calculated the two-electron distribution
0.8 eV or less for all the states shown in Table I. functions and the DIE spectra of Ar, CO, CO2, and C2H2 and
The column of U denotes the matrix element of the discussed the relations between them. We treated the two-
bare Coulomb interaction carrying the largest contribution to particle Greens function G2 by using the first principles
the DIEs. On the other hand, the actual Coulomb interaction, T-matrix theory to describe the short-range electron correla-
the difference between the T matrix and GWA 2 tions. The calculated two-electron distribution functions,
E E, which includes the effect of the multiple scatter- which include the multiple scatterings via the evaluation of
ings, is deviated from U by 1.5 3.4 eV. the ladder diagrams up to the infinite order, clearly indicate
the Coulomb hole. Moreover, we explained the relationship
between the short-range electron correlations the difference
D. C2H2 between + E + E and U and the Coulomb hole in
detail. In the cases of an isolated Ar atom and CO molecule,
The two-electron distribution functions without and with
in particular, we found that the electron distribution is af-
the interaction in the 5 level i.e., HOMO 1 of the C2H2
fected by the other electron and may in some cases concen-
molecule are plotted on a molecular plane as shown in Fig. 5.
trate on the atomic nucleus to screen its positive charge.
The four closed circles denote hydrogen, carbon, carbon, and
For the CO2 molecule, we presented new results of the
hydrogen atoms from top to bottom. To compare the two-
first ionization potential and the DIE spectra and compared
electron distribution function with the interaction shown in
them with the corresponding experiments as well as our pre-
Fig. 5b with the two-electron distribution function without
vious study on other molecules.5 The calculated first ioniza-
the interaction shown in Fig. 5a, we fix one electron at the
tion potential and DIEs for the CO2 molecule are in good
point marked by the cross near the hydrogen atom in Fig.
agreement with the experiments. The short-range electron
5b. A significant decrease in electron distribution around
correlations play an important role in the determination of
the fixed electron is observed. On the other hand, there is an
the double ionization energies. Again, we confirmed that the
increase in the electron distribution around the upper carbon
T matrix well describes the short-range electron correlations
atom at the opposite side of the fixed electron. We confirm
between two particles.
the Coulomb hole around the fixed electron and the shift in
the electron distribution from the CH of the fixed electron
ACKNOWLEDGMENTS
side to the CH of the opposite side.
The change in the electron distribution is considerable The authors are grateful to the Information Initiative
and is caused by the short-range electron correlation that is Center, Hokkaido University, for the use of the HITACHI
clearly indicated by the difference with the bare Coulomb SR8000 and SR11000 supercomputing facilities. This work
interaction U=12.8 eV with = = HOMO 1. The has been partly supported by Grants-in-Aid of the Scientific
actual Coulomb interaction + E + E is about 8.8 eV. The Research B No. 17310067 and Scientific Research on Pri-

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114108-6 Noguchi, Ishii, and Ohno J. Chem. Phys. 125, 114108 2006

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