N-body Quantum Eigen Matrix Elements Closed Form - Complete Basis

Wade Smith, zmth@yahoo.com

Florida Institute of Technology

Abstract : In (similar to) Hermite-Gaussian functions the matrix elements of a general n

body non-relativistic Hamiltonian quantum eigenfunction problem for bound states can be
evaluated(integrated) in closed form and the formation of a complete basis is straightfor-
ward. Also what is generally approximated in the shell model and denoted by the familiar
phrase 'spin-orbit coupling' can also be evaluated in closed form. We will generally work
in atomic units. We emphasize this is mainly of theoretical and possible analytic interest
only and not presented as a practical way of solving eigenfunction problems in quantum
chemistry as the computational load and storage rises exponentially as nn where n is of
the order of the total number of particles and most conventional methods make use of the
large ratio of nuclear to electron mass.
Key words : Non-relativistic, closed form, quantum chemistry, n body ,Hermite-Gaussian.

_________________________________________________________

In what follows assume reader is familiar with Dirac's bra/ket terminology and unless
otherwise noted consider all quantities real and assume nps > 1. Consider nps + 1 particles
of arbitrary masses and charges mi , qi such that a bound state exists. Separating out the
3 center of mass coordnates a general non-singular linear transformation to 3nps 'internal'
or relative cartesian coordinates yis in terms of original real particle coordinates xis may
be written
nps
(1)
X
yis = ai,j (xjs − x(nps+1)s )
j=1

Here s denotes one of the 3 cartesian coordinates and the transformation matrix is the same
for each of the 3 cartesian coordinates for a given particle number index. The (nps + 1)
particle index may be chosen arbitrarily. Also in (1) index j is a real coordinate index or
particle number and i may be called a 'pseudo' particle index but in the following will often
just use 'particle' when actually it is meant to be one of the nps pseudo particles when
the context is clear. Let c be inverse of matrix a and for convenience change(substitute)
notation xis for yis above. Any one of the nps(nps + 1)/2 interparticle potentials may be
written as one of the forms
qi qj qj q(nps+1)
qP , qP (2)
3 P P 2 3 P 2
s=1 ( k cj,k xk,s − k ci,k xk,s ) s=1 ( k cj,k xk,s )

where i, j, k range 1 thru nps. Of relevance now is the denominators of all interparticle

1
potentials are of form
1
qP (3)
3 Pnps
s=1 ( i=1 pi xis )2
, for some constants pi .
Using the identity
Z ∞ √
π
(4)
2
e−xu du = √
0 2 x
an interparticle potential may be written as product of charges times an expression of the
form
nps nps nps
! !
Z ∞
2 X X X
√ exp − ( pi xi1 )2 + ( pi xi2 )2 + ( pi xi3 )2 u2 du
π 0 i=1 i=1 i=1
  !2 
Z ∞ 3 nps
2
(5)
Y X
=√  exp − pi xis u2  du
π 0 s=1 i=1

Basis functions can be expressed as sums of products (times certain constants) of terms
of form
3 nps
(6)
Y Y 2
is −ai xis /2
xm
is e
s=1 i=1

where the ai are arbitrary nite positive and the mis are non negative integer exponents
generally ranging zero to innity. Assuming valid to interchange order of integration a bra-
ket matrix element of an inter particle potential will be constants times sums of products
of form
nps
" 3 Z
! #
Z ∞ Z
2 −( nps pk xks )2 u2 mis −ai x2is
(7)
Y P Y
√ ··· e k=1 xis e dx1s . . . dx(nps) s du
π 0 s=1 i=1

where here mis is the SUM of the corresponding exponent in bra plus that of ket. For 2
unit charges using the basis (6) it will be exactly (7). We rst do each of the 3 cartesian
nps fold integrations separately which can be done in closed form and generally yield 3
nps
!
pi 2
dierent irrational epressions each of form a power series in u times 2
raised
X
2
u +1
1
ai
to half a negative odd integer power. Integrating the product of these 3 over u has a closed
form solution because ai , pi are same for the 3 cartesian coordinates. Note in (6) if using
only a nite basis approximation we could in addition have several dierent ai series, as
long as same for each rectangular coordinate, because the matrix element would still be of
same form (7) with only a change in the positive denite ai values but would generally be
over-complete for an innite number of bais functions. There will be more detail and expla-
nation and examples of these closed form expressions later along with other considerations.

2
 For now some readers may nd the rest of this dissertation rather obvious, along with
closed form evaluation of kinetic energy and normalization integrals which are simpler
than the interparticle potentials. He may also have his own methods, applications and
explanations likely more ecient so can stop here. The detail of the author's evaluation
of (7) and to facilitate programming is correct but somewhat unclear and inecient so
will delay that to the end. Alternately the reader may be satised to use symbolic math
software (Maxima was used here) to show (7) can be integrated in closed form though may
have to manually separate the problem into several parts.
Basis functions are formed in a common way expressed as sums of products of func-
tions of each (pseudo)particle alone. To form a complete basis it is found convenient to
rst use spherical coordinates for each particle individually. Here we form only continu-
ous along with all derivatives basis functions so for any nite basis approximation cusp
conditions will not be satised but only approached in the limit as the number of basis
functions approaches innity in all 'directions'. In the following assume total angular mo-
mentum zero of spinless particles and no symmetry requirements. Aside from a ri ei e−ai ri /2
2

factor (ei a non negative integer) consider each particle as a certain spherical harmonic
nps
YLi ,mi , 1 ≤ i ≤ nps. Denote ei by the term total radial order. Using Louck we rst
X

i=1
nd all possible ways of combining, enumerating, the nps incoming Li so that the total
resultant angular momentum is zero. As explained Louck this generally involves some
enumeration over an additional nps−2 non negative parameter eigenvalues denoted as ki
in the text. Since we are assuming zero total angular momentum can reduce the number
of ki parameters to nps − 3. For example can use any one of diagrams (2.88) p110. Below
we use the rst diagram for example for nps = 4. In the gure and some notation below
will alternately use the more general symbol ji in place of Li . Then we use the methods of
Louck involving the Clebsch-Gordon coecients of the rotation group etc. denoted here
as eg. Cm
j1 j2 k1
1 m2 q1
to nd the actual sums of products of the various mi in YLi ,mi to eect
the complete zero total orthonormal angular momentum eigenfunctions.

3
j1m1 j2m2
\ /
k1q1 j3m3
\ /
k2q2 j4m4 j1 j2 k 1
Cm Cqk11m
j3 k2
Cqk22m
j4 j j1 j2 k 1
= Cm Cqk11m
j3 k2
C-mj44 m
j4 0
here
1 m2 q1 3 q2 4m 1 m2 q1 3 q2 40

\ /
jm

In the gure jm is 00, k2=j4 so k2 need not be considered. Anyway enumerating all
the possible ji , ki for zero total angular momentum is straightforward and programmable
for any nps as we have done in both maxima and fortran by making continued use of
'triangle conditions' in binary coupling of angular momenta. If not concerned with actual
values of ki but only in that they eect orthogonality for dierent multi-choices then
we may only need do assignments for a set of ji not connected by permutations such
as j1 ≤ j2 . . . jnps−1 ≤ jnps as any distinct permutations will also be orthogonal for the
nps
same ki set. For example if let ji = 2np and nps = 4 and write the tuples in format
X

i=1
[j1 , j2 , j3 , j4 , k1 ] then all possibilities for np = 1 are : [0,0,1,1,0], [0,1,0,1,1], [0,1,1,0,1],
[1,0,0,1,1], [1,0,1,0,1], [1,1,0,0,0] . For np = 2 : [0,0,2,2,0], [0,1,1,2,1], [0,1,2,1,1], [0,2,0,2,2],
[0,2,1,1,2], [0,2,2,0,2], [1,0,1,2,1], [1,0,2,1,1], [1,1,0,2,2], [1,1,1,1,0], [1,1,1,1,1], [1,1,1,1,2],
[1,1,2,0,2], [1,2,0,1,1], [1,2,1,0,1], [2,0,0,2,2], [2,0,1,1,2], [2,0,2,0,2], [2,1,0,1,1], [2,1,1,0,1],
[2,2,0,0,0]. By the prescription of Louck all 27 of these correspond to orthonormal zero
total angular momentum 'eigenfunctions'. Using Clebsch-Gordan for the rotation group
etc. the eigenfunctions of 0 total angular momentum for each of these individually can
be found in a straightforward way and have written maxima and fortran subroutines to
do such for general np, nps. Note in the condition of both np > 1 and nps > 3 there are
multiple orthonormal eigenfunctions for some of the same nps length series of Li tuple
values which correspond to dierent ki tuples.
The non-relativistic Hamiltonian eigen problem separates into those of total radial
order even or odd as the reader may verify now or later. The matrix element integral
is zero for the direct normalization, kinetic energy and interparticle potentials if the bra
is not of same parity as ket. When put in terms of rectangular coordinates it must be
true for each of the 3 coordinates individually (though NOT for 'spin orbit' interaction) -
sum of the 2nps exponents of bra plus ket must be even. Later will be shown that 'spin
orbit' interaction is also closed form integrable in this formulation and obeys same parity

4
restriction as far as sum of exponents over all 3 rectangular coordinates but not for each
individually and it's matrix elements are with respect to angular functions of total angular
momentum not equal 0. We are not considering electromagnetic eld interaction in terms
of emission/absorption of photon in which case there could be (?) transition from odd to
even etc. From here on for demonstration we consider only the even case and denote by the
nps
term total radial order ei = 2npmx . The even case is usually though not always the ground
X

i=1
state and the odd case must always be considered if need all eigenfunctions. In order to
nps
satisfy continuity of all derivatives Li must be even and is the minimal total radial order
X

i=1
associated with the particular zero total angular momentum function because each YLi ,mi
must be multiplied by riLi . All basis functions involving this zero total angular momentum
function are then formed by multiplying it by all possible combinations of powers of the
ri 2 - in addition to the xed riLi e−ai ri /2 factors. For example if Li = 2np then for this
2 X

np the total number of basis functions involving a single zero total angular momentum
eigenfunction of homogenous total radial order 2npmx, npmx ≥ np is npmx−np+nps−1
 
nps−1
and for all orders up through 2npmx the total is npmx−np+nps . To further indicate that
 
nps
these methods do yield a complete basis we enumerated all those of several even total
homogenous orders and various nps and compared that with the number obtained for
all possible even invariants in rectangular coordinates using USCLouck.tex Ang.Mom.in
qp307(6.152) (after accounting for the dependancies in that formula which occur when
both nps>3 and npmx>3) and the two agreed in all cases. If we choose to orthonormalize
then we only need do so in the scalar radial space(s) for each unique angular function
separately since the dierent zero total angular momentum functions are automatically
orthonormal by the prescription of Louck above. For example the only total radial order
nps
0 basis function is some normalizing constant times e−ai ri /2 and how to enumerate a
Y 2

i=1
complete orthonormal basis in general should be clear.
Consider one of the particular orthonormal zero total angular momentum eigenfunc-
tions written as
nps
(8)
X Y
cp YLi ,mip(θi , φi ).
p i=1

Including the radial part a basis function associated with this angular function will contain
terms and may be written
nps
(9)
X Y 2
cp riLi +2si e−ai ri /2 YLi ,mip(θi , φi ).
p i=1

where the si tuples range 0 to innity in all indices. Regardless of the si tuples, basis
functions associated with dierent angular eigenfunctions will still be orthogonal with
respect to the direct integral. The same may not in general be true of a kinetic energy
matrix element because when transform the kinetic energy operator from the real nps+1
original particle coordinates to nps internal coordinates cross partials in particle number
indices such as ∂ 2 /(∂θi ∂θj ), j > i, and others occur. Regardless of this issue, matrix

5
element integrals can be evaluated in closed form. But if we also would like the kinetic
energy operator to remain orthogonal if associated with dierent angular eigenfunctions
of total angular momentum 0 regardless of the si tuples all that needs to be done is put
simple conditions, as will show later, on the transformation matrix of the new coordinates
in terms of the old, (1), so that cross partials in dierent particle indices do not occur. In
spherical coordinates
L(L+1)f (r) ∂ 2 f (r) 2 ∂f (r)
 
−∇2 (f (r)YL,m ) = − − YL,m (10)
r2 ∂r2 r ∂r

which does not depend on m. Since all the terms in the sum in (9) are for the same Li
tuple the ratios of the cp remain the same so it is the same angular function just multiplied
by a dierent radial function. So in this case for both the direct and kinetic energy matrix
element integrals the angular part just integrates to unity and the pertinent integrals
needed for kinetic energy and normalization are one dimensional and from (10) are of
form
∞
L(L+1)fk (r) ∂ 2 fk (r) 2 ∂fk (r)
Z  
r2 fb (r) − − dr (11)
0 r2 ∂r2 r ∂r
(12)
2 2
fb (r) = rL+2s1 e−ar /2
, fk (r) = rL+2s2 e−ar /2

for bra and ket and s1, s2 are arbitrary non negative integers and a arbitrary positive
denite. The pertinent direct integral needed is
√
∞ Γ(s1+s2+L+ 23 )
Z
π(2(s1+s2+L)+1)!!
r(2L+2(1+s1+s2)) exp(−ar2 )dr = =
s1+s2+L+ 3 3
0 2a 2 2s1+s2+L+2 as1+s2+L+ 2
and using some integration by parts with help of maxima (11) evaluates to
 
1+2s1+2s2+2L
2

Γ 2
4(s1+s2 −(s1−s2) +L(L+2))+3 1
8as1+s2+L+ 2
2


√ 4(s1+s2 −(s1−s2) +L(L+2)) + 3 |2(s1+s2+L) − 1|!!
= π 1 .
2s1+s2+L+3 as1+s2+L+ 2
Still considering the case of no cross partials, in one of the fortran programs for the
complete Hamiltonian matrix and to nd largest magnitude of bound state eigenvalues by
the regular power method, we needed the matrix element of 1+KE where KE is kinetic
energy. Let ki,i be the coecient of −∇i 2 for (pseudo) particle i (eg in the case of nps = 1,
which we are NOT considering, would have k1,1 = m1 +m2 ). Then the pertinent matrix
2m1 m2
element of 1+KE from above is
 
nps
nps Y (2(Li +s1i +s2i ) + 1)!!
π 2  
s1i +s2i +Li + 3
i=1 2s1i+s2i+Li+2 ai 2

nps
! !
X ai ki,i 4(s1i +s2i −(s1i −s2i )2 +Li (Li +2)) + 3
∗ +1 (13)
i=1
4(s1i +s2i +Li ) + 2

where again s1i , s2i are the respective powers of ri 2 in bra,ket or vice versa.
As mentioned prior theoretically if the number of basis functions is innite and complete
it doesn't matter what is matrix a nor the positive denite parameters ai . For a nite basis
approximation all of these considerations do make a dierence and there are no clear choices
which are best in any sense. Using the form (1), the following nps(nps−1)/2 conditions

6
insure there are no cross partials for KE in the internal reduced coordinates :
nps Pnps Pnps
ai,k aj,k ( k=1 ai,k )( k=1 aj,k )
(14)
X
+ = 0 f or all j > i.
mk mnps+1
k=1

The values of the ki,i , coecient of −∇i 2 , are equal 1/2 times left side of (14) but with
j = i. We give a couple of 'easy' triangular matrix examples for the matrix a in (1) for
general nps which obey (14) and ki,i and pi in (3) , which are all that are needed, are
automated functions of particle masses here denoted as mi . First assume matrix a lower
triangular with all diagonals unity. For i > j,
mj
ai,j = − Pi−1 . (15)
m(nps+1) + k=1 mk

The inverse matrix c is also lower triangular all diagonals 1 and

mj
ci,j = Pj , i > j. (16)
m(nps+1) + k=1 mk

Note the matrices do not depend upon mnps . From left side (14) times 1/2, i = j
Pi
(m(nps+1) + k=1 mk )
ki,i = Pi−1 . (17)
2mi (m(nps+1) + k=1 mk )

From (2) we nd the nps tuple pi for each of the nps(nps + 1)/2 interparticle potentials
in (3). For the rst of (2) assume j > i and use notation pk rather than pi for clarity.
pk = 0, k < i or k > j
m(nps+1) + i−1
P
n=1 mn
= Pi ,k = i
m(nps+1) + n=1 mn
mk
= , i<k<j
m(nps+1) + kn=1 mn
P

= 1, k = j. (18)

For the second of (2) 1 ≤ j ≤ nps the pk are row j of the c matrix,
mk
pk = , k<j
m(nps+1) + kn=1 mn
P

= 1, k = j
= 0, k > j. (19)

Next we just divide the rows of the a matrix by function of masses so that all ki,i = 1/2.
s
mi
ai,j = −mj Pi−1 Pi , j <i
(m(nps+1) + k=1 mk )(m(nps+1) + k=1 mk )
v
u mi (m(nps+1) + i−1
u P
k=1 mk )
=t Pi , i = j. (20)
(m(nps+1) + k=1 mk )

The inverse matrix elements are

s
mj
ci,j = Pj−1 Pj , j <i
(m(nps+1) + k=1 mk )(m(nps+1) + k=1 mk )
v
u (m(nps+1) + ik=1 mk )
u P
= t , i = j. (21)
mi (m(nps+1) + i−1
P
k=1 mk )

7
For example for nps = 4 the elements of matrix c are
r
m5 +m1
0 0 0
m1 m5
s s
m1 /m5 m5 +m1 +m2
0 0
m5 +m1 m2 (m5 +m1 )
s s s
m1 /m5 m2 /(m5 +m1 ) m5 +m1 +m2 +m3
0
m5 +m1 m5 +m1 +m2 m3 (m5 +m1 +m2 )
s s s s
m1 /m5 m2 /(m5 +m1 ) m3 /(m5 +m1 +m2) m5 +m1 +m2 +m3 +m4
m5 +m1 m5 +m1 +m2 m5 +m1 +m2 +m3 m4 (m5 +m1 +m2 +m3 )

The automated expressions for the pk tuples for general nps > 1 in (3) for the interparticle
potential between particles i, j are found from the dierences of pairs of rows i, j of (21)
pk = 0, k < i or k > j
v
u m(nps+1) + i−1
u P
n=1 mn
=t ,k = i
mi (m(nps+1) + in=1 mn )
P
s
mk
= , i<k<j
(m(nps+1) + k−1 )(m(nps+1) + kn=1 mn )
P P
n=1 m n
v
u m(nps+1) + jn=1 mn
u P
= t , k = j. (22)
mj (m(nps+1) + j−1
P
n=1 mn )

Again for the second of (2) 1 ≤ j ≤ nps the pk tuple is row j of matrix c of (21). Note in this
case (13) does not depend upon the particle masses nor charges. The only dependance on
masses and charges is product of charges times terms of form (7) where the pk tuples there
are function of masses per the particular i, j, j > i indices combination or of the 1 ≤ j ≤ nps
index alone in 2nd of (2). The other constants multiplying dierent forms of types (7) are
just those of converting spherical coordinates to rectangular and also dependant upon the
arbitrary ai , the value of nps, etc. but are not function of masses and charges of particles.
The magnitude of the bound state eigenvalues are of homogenous order 1 in the masses
and order 4 in the charges so if all masses are multiplied by some postive real number the
bound state eigenvalues are multiplied by the same. These statements are not generally
true if 'spin orbit' interaction is included.

There are many analytic ways and algorithms for solving (7). It is not the most
direct nor ecient way but will here do in part by using similar to nding coecients in
generating functions. With help of maxima, disregarding integral over u for now, express
a single rectangular component of (7) by
Z Z nps Pnps
2
pk xk )2 u2
Y
··· ebi xi −ai xi e−( k=1 dx1 . . . dxnps =
i=1
b2 2 2 2
b2
!
Pnps i pj −2bi pi bj pj +bj pi
)u2 + nps i
P
i,j>i ( ai aj i ai
exp 4(
Pnps 2
)
( i=1 pi /ai )u2 +1
(23)
nps
π 2 p Qnps Pnps 2 ,
( i=1 ai ) (( i=1 pi /ai )u2 + 1)
dierentiate with respect to each bi , mi times and afterwards set all bi = 0. We don't go
into much detail in the following because the reader may well have a more concise ecient

8
solution. If interested in more detail one may try to decipher the fortran subroutines in
appendix and/or email the author. Thinking in terms of nps(nps +1) variables bi bj , j ≥ i
2
with j ≥ i in the numerator of the exponent then the coecient of b2i is
p2
j
)u2 +1
P
( j6=i aj
(24)
ai
and of bi bj , j > i in the numerator is
pi pj
−2u2 . (25)
ai aj
The other quantities in (23) may be regarded as overall constant multipliers including
among others the denominator of the exponent of the exponential which , for a non zero
result, is raised to the integer n which equals half the sum total of the mi which is the total
2
number of times the exponential will be dierentiated with respect to the various products
bi bj , j ≥ i. Expanding the exponential power series about the exponent at 0 the only terms
which survive after dierentiations with respect to the bi , mi times and afterwards setting
all bi = 0 are all contained in that power of the exponent of the exponential raised to the
n
power where n = mi , the total even power for the particular rectangular component
X
2
nps
and we are looking for the coecient of
Y
bm
i .
i

i=1
nps(nps+1)
Denote a certain multinomial term in the variables bi bj , j ≥ i as
2
nps(nps+1)
2

(26)
Y
vkpk .
k=1

Here vk = bi bj for index k unique to i, j combination. The power tuple pk in (26) which
nps
will yield a given multinomial term in the bi that is mi
, for a certain mi sequence, is
Y
bi
i=1

not unique. Use an iterated nps(nps−1) fold summation over all the possible combinations
2
of powers of the bi bj , j > i to nd all possibilities - the powers of the b2i will then be xed.
Anyway after going through all this the product for all 3 rectangular coordinates can be
expressed as a power series in u2 times a common factor
nt 3nps
(−1) 2 π 2
nt Qnps 3 Pnps 2 nt 3 . (27)
2 2 ( 1 ai ) 2 ( 1 paii u2 + 1)( 2 + 2 )
3,nps
where nt = mis is even. To obtain the nal answer integrate over u from 0 to innity.
X

s,i
From maxima nd
∞ −(s+ 12 )
ap β(s+ 21 , −s+m+1)
Z
2s 2
u (ap u + 1) −(m+ 23 )
du = , m≥s (28)
0 2
nps
pi 2 nt
and applied here with ap = the integral equals
X
, m=
1
ai 2

−(s+ 21 ) nt nt
ap (2 − s)!2( 2 −s)
Q nt2 . (29)
i=s (2i + 1)

9
Since the nal answer must be homogenous order -1 in the pi the coecients of the various
powers of u2 in the power series must be of homogenous order in the pi of twice the power
of u2 . A fortran subroutine to evaluate √2 times expression (7) has been compiled and
π
tested and is given in appendix. There are symmetries other than invariance to the 6
permutations of the 3 rectangular coordinates. For example for each of the nps particles
the nal answer only changes sign under change of sign of pi in (3) according to whether the
3
sum of it's corresponding 3 exponents , mis where mis is the sum of the corresponding
X

s=1
3
exponent in bra plus that of ket, is odd or even (eg if any pi = 0 and mis is odd the
X

s=1
nal result is always 0).
The development in the last two paragraphs is general in nding matrix elements of
the coulomb potential in basis (6) and not restricted to matrix elements between total
(orbital)angular momentum zero functions. For example the spatial part of 'spin orbit'
interaction may be written as sums of some (generally complex) constants times rectan-
gular components of VxE where V, E are velocity,electric eld 3-vectors and x is cartesian
cross product. Consider the contribution of the y or 2nd component of electric eld at one
of the original nps+1 real particles say particle j (for simplicity now consider j < nps+1
though that case could also be easily computed) due to a certain interparticle potential.
In relative reduced coordinates from (5), aside from from an overall constant multiplier
and for now disregarding the intergral over u, obtain the form
 !2 
nps nps
! 3
(30)
X Y X
2u2 pi xi2 exp − pi xis u2 
i=1 s=1 i=1

as the pertinent term for the y or 2nd component of electric eld where the pi tuple
depends upon j and the other particle of the interparticle potential via the matrix c per
(3) from (2). Now we need the velocity 'operator' acting on (6). Consider the x or 1st
√
component of velocity of particle j. Omitting an imaginary −1 factor obtain
3 nps
! nps
mi1
(31)
Y Y 2 X
is −ai xis /2
xm
is e ai,j (ai xi1 − )
s=1 i=1 i=1
xi1

to be divided by the mass of particle j where the ai,j are the elements of the transform
matrix in (1) and the unrelated arbitrary positve ai are as in (6). So for this particle
the pertinent contribution(aside from some constant multiplier) of a certain interparticle
potential to the 3rd or z component of VxE is just the product of (30) and (31) after
integrating over u. It is clear that after multiply by a bra of same form (6) and integrating
over all spatial coordinates this product results in a sum of essentially the same integrals
(7),except here du is replaced by u2 du,considered in the prior 2 paragraphs for the in-
terparticle potentials so can be evaluated the same way in closed form. Note the above
may not have been exactly correct as likely should have subtracted the velocity of the

10
other particle in the interparticle potential (assuming it's not particle nps+1) to get the
relative velocity etc. but still should be of the same type integrals in the prior 2 paragraphs.

Appendix

A fortran 2003 program code le "pem.F03" follows. It was compiled by gfortran with
DOS command line "gfortran -O3 -ast-math pem.F03" which makes an executable le
named a.exe. One could eliminate or change the alternate switches ' -O3 -ast-math '.
For example just use "gfortran pem.F03". In our case all was done using 64 bit windows 7
compiled and run in the dos environment. If one were to use other compilers may have to
modify somewhat - eg in pertinent places where the code reads 'end' may have to replace
with 'end subroutine' or 'end "name of subroutine" ' etc.. Anyway the coulomb potential
matrix element output is the integral (7) expressed as a single precision real number and
written to the dos screen and also appended to a le named pem.t (arbitrary previously
existing le) after the word "pem". There must rst exist an input le named readpem.t
of following format. The rst entry rst line of the le must be nps and it ignores all
entries after atleast one space after the rst entry . The next ve lines must have atleast
nps entries each and ignores all entries after the rst nps on each of those lines and there
should be a 7th blank line or any number greater than one lines of any 'junk after the rst
6 lines. The 2nd thru 4th lines are respectively for each of the 3 rectangular coordinates:
sum of the exponents of bra plus ket for each of the nps (pseudo)particles, mis of bra plus
mis of ket in (6). The 5th line are the ai entries in (6) and the 6th are the pi of (3).

module inc
parameter (pi =3.1415926535897932)
integer*1 i,ia,ir,j,k,n,np,npmx,nps
integer*2 iu
real tb
contains
subroutine binomrs(n,id,r) ; integer*1 n,i,id,j ; j=max(id,n-id)
if(j<=n) then ; r=1. ; do i=1,n-j ; r=r*(n-i+1)/i ; enddo
else ; r=0;endif ; end
subroutine ffr(i,r) ; integer*1 i , j
r=real(i) ; do j=i-2,2,-2 ; r=r*j
enddo ; end
end module inc

use inc
integer*1,allocatable::d2lis(:),lisi(:),lisin(:),lo(:)
allocatable::alis(:),pai(:),rp(:),u2lis(:),u2ls(:)
call cpu_time(start)

11
open (1, file="readpem.t",status="old",position="rewind",action="read",iostat=ierror)
open (2, file="pem.t",status="old",position="append",action="readwrite",iostat=ierror)
write(2,*)"______________________________________"
read(1,*) nps ; print*," pem.F03 ,nps",nps
write(2,*)" pem.F03, nps",nps
i=1; j=2; t=0
allocate(lisin(3*nps))
read(1,*)lisin(:nps)
read(1,*)lisin(nps+1:2*nps)
read(1,*)lisin(2*nps+1:)
if(mod(sum(lisin(:nps)), j)==i)then
write(2,*)"x component sums odd",lisin(:nps)
print*,"x component sums odd",lisin(:nps)
elseif(mod(sum(lisin(nps+1:2*nps)), j)==i)then
write(2,*)"y component sums odd",lisin(nps+1:2*nps)
print*,"y component sums odd",lisin(nps+1:2*nps)
elseif(mod(sum(lisin(2*nps+1:)), j)==i)then
write(2,*)"z component sums odd",lisin(2*nps+1:)
print*,"z component sums odd",lisin(2*nps+1:)
else
npmx=(sum(lisin)+2)/4
allocate(alis(nps),d2lis(nps),lisi(nps),lo(nps),pai(nps)&
,rp(nps),u2lis(2*npmx+1), u2ls(2*npmx+1))

read(1,*)alis
read(1,*)rp
call pem(alis,d2lis,lisi,lisin,lo,pai,rp,t,u2lis,u2ls)
write(2,*)"x",lisin(:nps) ; print*,"x",lisin(:nps)
write(2,*)"y",lisin(nps+1:2*nps) ; print*,"y",lisin(nps+1:2*nps)
write(2,*)"z",lisin(2*nps+1:) ; print*,"z",lisin(2*nps+1:)
write(2,*)"alis",alis ; print*,"alis",alis
write(2,*)"rp",rp ; print*,"rp",rp
endif
20 write(2,*)"pem",t ; print*,"pem",t
write(2,*)"End pem.F03 nps",nps
print*, "End pem.F03 nps",nps

write(2,*)"with command line switches -O3 -ffast-math "

call cpu_time(fin); print*, "TIME",fin-start
write(2,*)"TIME",fin-start
end

subroutine pem(alis,d2lis,lisi,lisin,lo,pai,rp,t,u2lis,u2ls)
use inc,only: ir,iu,npmx,nps,pi
integer*1 d2lis(nps),i,ii,j,k,lisi(nps),lisin(3*nps),lo(nps),ntop
integer*2 lena,lenb,iu0
real alis(nps),pai(nps),rp(nps),u2lis(1+2*npmx),u2ls(1+2*npmx)
iu0=0; ! order format of lisin of length 3*nps is rect coord 1
do k=0,2 ; iu=0 ! for all nps particles, next 2nd rect coord for all nps
do i=1,nps ! ,last nps entries are rect coord 3
iu=iu+lisin(k*nps+i);enddo ! i=1,nps
if(iu>0) then ; u2lis(1:iu/2+1)=0 ; lena=iu/2+1

12
 call pmb(alis,lisi,lisin(k*nps+1:(k+1)*nps),lo,pai,rp)
iu0=iu0+iu ; i=1 ; j=0
call d2enum(alis,d2lis,i,lisi,lo,j,pai,1.,rp,u2lis)
else ; u2lis(1)=1 ; lena=1;endif ! iu>0
if(k==0) then
u2ls(1:lena)=u2lis(1:lena) ; lenb=lena
else; u2ls(lenb+1:lenb+iu/2)=0;lenb=lenb+iu/2
do i=0,iu0/2 ; r=0
do j=max(0,i-iu/2),min(i,(iu0-iu)/2)
r=r+u2ls(iu0/2+1-iu/2-j)*u2lis(iu/2+1-i+j)
enddo!
u2ls(iu0/2+1-i)=r
enddo! i
endif ! k==0
enddo
a1=0 ; do i=1,nps ; a1=a1+rp(i)**2/alis(i);enddo
t=u2ls(iu0/2+1) ; do i=0,iu0/2-1
t=u2ls(iu0/2-i)+t*(iu0-2*i-1)/a1/2/(i+1) ; enddo
r=alis(1);do i=2,nps ; r=r*alis(i);enddo
r=r*sqrt(r);
if(iu0>0) then ; r=r*3 ; do i=2,iu0/2
r=r*(2*i+1)
enddo;endif;r=r*sqrt(a1)
t=t*2*pi**((3*nps-1.)/2)/r
if(iu0>0) then
r=iu0/2
do i=iu0/2-1,2,-1 ; r=r*i ; enddo ; t=t*r
i=(-1)**(iu0/2)
if(i<0) then; t=-t ; endif;endif
end

recursive subroutine d2enum(alis,d2lis,ii,lisi,lo,ntop,pai,rin,rp,u2lis)

use inc,only:binomrs,ffr,ia,ir,iu,npmx,nps,tb
integer*1 d2,d2lis(nps),i,ii,j,lisi(nps),lo(nps),m,n1,n1r,ntop,ntp
real alis(nps),pai(nps),rp(nps) ,u2lis(1+2*npmx)
n1=lisi(ii)
if(ii==ir) then
d2lis(ii)=(n1-ntop)/2 ; ia=iu/2
do i=1,ii; ia=ia-d2lis(i);enddo
tb=rin; do i=0,ntop-1
tb=tb*(n1-i);enddo
j=abs(n1-ntop-1); call ffr(j,r) ; tb=tb*r
do i=1,ii; tb=tb*alis(lo(i))**(d2lis(i)-lisi(i));enddo
j=(-1)**sum(d2lis(1:ii));if(j<0) then;tb=-tb;endif
do i=1,ii;if(lisi(i)>2*d2lis(i)) then
tb=tb*rp(lo(i))**(lisi(i)-2*d2lis(i));endif;enddo
j=1; call tpd2(d2lis,j,j,pai,1.,u2lis)
else
n1r=sum(lisi(ii+1:ir))
do ntp=max(0,ntop-n1r),min(ntop,n1)
call binomrs(ntop,ntp,r);rnnt=r
do i=0,ntp-1;rnnt=rnnt*(n1-i);enddo

13
 do d2=max((n1+ntop-n1r)/2-ntp,0),(n1-ntp)/2
d2lis(ii)=d2
j=abs(2*d2-1);call ffr(j,r);rn=rin*r
j=2*d2
call binomrs(n1-ntp,j,r);rn=rn*r*rnnt
m=ntop+n1-2*(d2+ntp);j=ii+1
call d2enum(alis,d2lis,j,lisi,lo,m,pai,rn,rp,u2lis);enddo
enddo
endif ; end

recursive subroutine tpd2(d2lis,i,mm,pai,rm,u2lis)

use inc,only:binomrs,ia,ir,npmx,nps,tb
integer*1 d2lis(nps),i,j,k,m,mm
real pai(nps),u2lis(1+2*npmx)
if(i<ir) then ; j=i+1 ; call tpd2(d2lis,j,mm,pai,rm,u2lis)
else ; u2lis(ia+mm)=u2lis(ia+mm)+rm*tb ; endif
do m=1,d2lis(i) ; call binomrs(d2lis(i),m,r)
tt=r*pai(i)**m
if(i<ir) then ; j=i+1 ; call tpd2(d2lis,j,mm+m,pai,rm*tt,u2lis)
else ; u2lis(ia+mm+m)=u2lis(ia+mm+m)+rm*tb*tt
endif ; enddo
end

subroutine pmb(alis,lisi,bblis,lo,pai,rp)
use inc,only: ir,nps
integer*1 i,i0,j,jj,lisi(nps),bblis(nps),lo(nps),tmp
real,dimension(nps):: alis,pai,rp
logical*1 fl1/.false./
lo=(/(i,i=1,nps)/) ; i0=1
10 jj=0
if(bblis(lo(i0+1))>bblis(lo(i0))) then
fl1=.true. ; j=1
do while(bblis(lo(i0+1+j))>bblis(lo(i0+j)).and.j<nps-i0)
jj=j ; j=j+1
enddo
do i=0,jj/2
tmp=lo(i0+i) ; lo(i0+i)=lo(i0-i+jj+1) ; lo(i0-i+jj+1)=tmp
enddo
endif
if(i0+jj<nps-1) then
i0=i0+jj+1 ; goto 10
else ; if(fl1) then ; fl1=.false.
i0=1 ; goto 10 ; endif ; endif
lisi=(/(bblis(lo(i)),i=1,nps)/)
ir=nps ; i=0
do while(lisi(nps-i)==0.and.i<nps-1)
i=i+1 ; ir=ir-1
enddo ; pai=0
do i=1,nps ; do j=1,i-1
pai(i)=pai(i)+rp(lo(j))**2/alis(lo(j)) ; enddo
do j=i+1,nps
pai(i)=pai(i)+rp(lo(j))**2/alis(lo(j)) ; enddo ; enddo

14
end

The simplest(not necessarily optimum) choice at least for zero total angular momen-
tum seems to be choosing the transformation matrix in (1) as the unit matrix. In this
case for all interparticle potentials at most 2 of the pi , (3) via (2), are non zero and equal
+ or minus 1. For the 1st of (2) the two non 0 values can be taken as 1,-1 and for the
2nd of (2) the single non 0 value may be set to 1. In this 2nd case (7) can be evaluated
using spherical coordinataes without having to go through all the transformation (23) and
ensuing paragraph there. Further if all ai are set equal then by an orthogonal transfor-
mation all the nps(nps − 1)/2 interparticle potentials rst of (2) can be expressed as a
linear sum over those in which only a single pi is non 0 and equal 1. If matrix a of (1) and
hence c of (2) is unit matrix then there will generally be cross partials to deal with in the
normalization.
Ofcourse the nps+1 index could be replaced by any linear combination of particles
X
bi x i
as long as bi = 1. Can combine the nps + 1 particles to form nps pseudo particles in
X

any way desired. If form the nps by nps+1 matrix a1 by expressing the rows of matrix a
as coe's of the nps+1 particles then the sum of the colums of matrix a1 is 0 for every row.

√ m1+m2+m3
2πa
(32)
X
n1! (2(m1+m2+m3−n1)+1)!! (−2)n1
8(4m1+m2+m3 )am1+m2+m3+3 n1=0
min( m1+m2 ,m1+m2+m3−n1) m1+m2−2n2
2
(−4)n2
 
m3
(33)
X X
(−1)n3
n2=0
2n2 + 1 n1−n3−n2
n3=max(0,n1−n2−m3)
  min(2n2,m2)   
m1+m2−2n2 m1 m2
(34)
X
n4
(−1) .
n3 2n2 − n4 n4
n4=max(0,2n2−m1)

If nps>2 then for the higher coord's use

w = w1,2 = cos(θ2 − θ1 ), w1,i = cos(θi − θ1 ),
w2,i = cos(θi ) cos(θ2 ) + sin(θi ) sin(θ2 ) cos(φi − φ2 ).

for dierentiations and for the nal integrations set θ1 = φ2 = 0. For the potential
1
p
ri 2 2
+ rj − 2ri rj wij

matrix elements just permute transform coord's to put i, j in the 1, 2 position.

Model nuclear strong force as also nucleon,protons,neutrons have in addition to coulomb
force/potential that due to multipole moments eg as per dipole moment would be propor-
tional to electric eld and higher Multipole moments in (30)

The main strategy consideration is to choose the innite set of possibilities in order to pos-
sibly deduce analytic and combinatorial/recursion relations which will also depend upon
the interparticle potential being expresssed ...Any of the diagrams could be used.Dierent
a0i s series but if to inf is over complete. Obvious drawback of Triangular formulation not
lend itself symmetrization - symmetry adapted. Perhaps in terms of even invariants may

15
make evaluation of potential more comprehensible if nd an analytic way to enumerate
the indep's. More fundamental reason integrable in closed form - lot more work needs to
be done. For a large class of problems should be able to apply symmetry requirements
on goups of identical particles as last resort expressing all in rect coords and setting all ai
equal. Not numerical integration nor truncation of an innite series.

_________________________________________________________

[1] Slater, John C Quantum Theory of Molecules and Solids volume 1 McGraw Hill 1963

[2] Jackson, J. D. Classical Electrodynamics , John Wiley & Sons ,Inc. 1962

[3] Kanwal, Ram P. Generalized Functions : Theory and Technique Academic Press 1983.

[4] E.G. Kalnins, W. Miller, Separation of variables on n-dimensional Riemanian mani-

folds. Journal of Mathematical Physics 27(7), July 1986

[5] Macsyma, a large symbolic manipulation program developed at the MIT Laboratory for
Computer Science and supported from 1975 to 1983 by grants from NASA and others...'82-
'92 by Symbolics of Burlington Mass. and since 1992 by Macsyma Inc. of Arlington, Mass.

- seems they have been out of business for several years as far as we can tell.

[6] Hildebrand Advanced Calculus for Applications , pp.143-153 , Prentice Hall 1962

[7] Schi, L. I. Quantum Mechanics McGraw Hill 3rd ed 1968 , 2nd ed. 1955

[8] Raymond Nepstad & Lene Saelin The n-dimensional coulomb problem... Dept.Physics
and Tech.Univ. Bergen, March 16, 2006

[9] P.M. Morse and H. Feshbach. Methods of theoretical physics McGraw-Hill NY 1953

[10] Jin-Quan Chen, Jialun Ping & Fan Wang Group Representation Theory for Physicists
1st edition World Scientic Pub. Co. 1989

[11] Edmonds, A.R. Angular momentum in quantum mechanics , Princeton University

Press

[12] Pauling and Wilson Introduction to Quantum Mechanics p. 247 , McGraw-Hill 1935

[13] C. D. Lin Correlation of excited electrons .The study of channels in hyperspherical

coordinates Phys Rev A , vol 10 , no. 6 , Dec. 1974.

[14] Xuguang Chi et al, sheng@ust.hk Kinetic energy operator approach to the quantum
three-body problem with Coulomb interactions arXiv:physics/0602139 v1 21 Feb 2006

16