XI Discrete Variable Representation

The goal of this section is to introduce a generic discrete variable representation (DVR) method, introduced by Colbert and
Miller [J. Chem. Phys. (1992) 96:1982-1991] to solve the time-independent Schr odinger equation,
HC
j
C
j
E
j
= 0, (80)
and obtain the eigenvalues E
j
corresponding to the eigenstates
j
(x) in a grid-based representation: (x) =

j
C
j
(x
x
j
). The DVR method simply evaluates the Hamiltonian matrix H in a discrete (grid-based) representation and obtains
the eigenstates and eigenvalues by using standard numerical diagonalization methods e.g., TRED2, TQLI and EIGSRT,
as described in Numerical Recipes (Ch. 11, Numerical Recipes), or Lanczos-type (iterative linear algebra methods) that
exploit the sparsity of H.
The rest of this section shows that the Hamiltonian matrix elements are:
H(j, j

) = V (x
j
)
jj
+

2
2m
(1)
jj

jj

2
3
+ (1
jj
)
2
(j j

)
2
_
, (81)
when the delta functions are placed on a grid x
j
= j that extends over the interval x = (, ) with j = 1, 2, ....
Furthermore, we show that for the particular case of a radial coordinate dened in the interval x = (0, ), the Hamiltonian
matrix elements are:
H(j, j

) = V (x
j
)
jj
+

2
2m
(1)
jj

jj

2
3

1
2j
2
_
+ (1
jj
)
_
2
(j j

)
2

2
(j +j

)
2
__
. (82)
In order to derive Eq. (81) and Eq. (82), we consider the Hamiltonian,

H =

T +V ( x), (83)
where V ( x) and

T =
p
2
2m
are the potential and kinetic energy operators. In the representation of delta functions (x x
j
),
equally spaced at coordinates,
x
j
= x
min
+j, (84)
33
with = (x
max
x
min
)/N, the potential energy matrix V
()
is diagonal with matrix elements dened as follows:
V
()
(j, k) = j|V ( x)|k =
_
dx

(x x
j
)V ( x)(x x
k
),
= V (x
k
)
j,k
.
(85)
In order to obtain the kinetic energy matrix T
()
in the same grid-based representation, we rst obtain the kinetic energy
matrix T
()
in the representation of eigenstates
n
(x) of the particle in the box x = (x
min
, x
max
). Then, we rotate T
()
to
the representation of delta functions by using the following similarity transformation:
T
()
= C
1
T
()
C, (86)
where C is the transformation matrix dened by the linear combinations,

k
(x) =

j
C(j, k)(x x
j
), (87)
where
C(j, k) =
k
(x
j
). (88)
The eigenstates of the particle in the box are:

k
(x) =
_
2
x
max
x
min
Sin
_
k
(x x
min
)
(x
max
x
min
)
_
, (89)
with
k
(x
min
) = 0 and
k
(x
max
) = 0. Therefore,

T
k
(x) =
(k)
2
2m

k
(x),
(90)
and T
()
is diagonal with matrix elements,

T
()
(j, k) =
j
|

T|
k
=
(k)
2
2m

2
(x
max
x
min
)
2

jk
. (91)
34
Therefore, substituting Eq. (91) and Eq. (88) into Eq. (86) we obtain,
T
()
(i, i

) =

j,k=1
C
1
(i, j)T
()
(j, k)C(k, i

) =

j,k=1
C(j, i)T
()
(j, k)C(k, i

),
=

2

2
(x
max
x
min
)
2

j,k=1

j
(x
i
)
(k)
2
2m

jk

k
(x

i
) =

2

2
(x
max
x
min
)
2

k=1

k
(x
i
)
(k)
2
2m

k
(x

i
),
=

2

2
2m(x
max
x
min
)
2
2
(x
max
x
min)

k=1
k
2
Sin
_
k
(x
i
x
min
)
(x
max
x
min
)
_
Sin
_
k
(x
i
x
min
)
(x
max
x
min
)
_
.
(92)
Finally, substituting Eq. (84) into Eq. (92) we obtain:
T
()
(j, j

) =

2

2
2m(x
max
x
min
)
2
2
N

k=1
k
2
Sin
_
kj
N
_
Sin
_
kj

N
_
. (93)
In order to calculate the innite sum analytically, we note that
2Sin
_
kj
N
_
Sin
_
kj

N
_
= Cos
_
k(j j

N
_
Cos
_
k(j +j

)
N
_
,
= Re
_
Exp
_
i
k(j j

N
_
Exp
_
i
k(j +j

)
N
__
.
(94)
Therefore, Eq. (93) can be written as follows:
T
()
(j, j

) =

2

2
2m(x
max
x
min
)
2
2
N
_
Re

k=1
k
2
Exp
_
i
k(j j

N
_
Re

k=1
k
2
Exp
_
i
k(j +j

)
N
_
_
. (95)
Evaluating the sum over k analytically, we obtain:
T
()
(j, j

) =

2
(1)
jj

2m(x
max
x
min
)
2

2
2
_
1
Sin
2
[(j j

)/(2N)]

1
Sin
2
[(j +j

)/(2N)]
_
, (96)
for j = j

and
T
()
(j, j) =

2
2m(x
max
x
min
)
2

2
2
_
(2N
2
+ 1)
3

1
Sin
2
[j/N]
_
. (97)
35
These equations are obtained by considering the geometric series

k=0
x
k
= 1/(1 x) and noting that:
x

x

k=0
x
k
=

k=0
kx
k
,
x
2

2
x
2

k=0
x
k
=

k=0
k
2
x
k

k=0
kx
k
.
(98)
Therefore,

k=1
k
2
x
k
=

k=0
k
2
x
k
,
= x
2

2
x
2
_
1
1 x
_
+x

x
_
1
1 x
_
,
=
2x
2
(1 x)
3
+
x
(1 x)
2
.
(99)
Equation (81) is obtained from Eq. (96) and Eq. (97), by taking the limit x
min
, x
max
, at nite . This
requires N . Furthermore, since (j + j

) = x
j
+ x
j
2x
min
and (j j

) = x
j
x
j
, this limit implies
(j +j

) while (j +j

) remains nite.
Equation (82) is obtained from Eq. (96) and Eq. (97), by making x
min
= 0, and taking the limit x
max
, at nite
. This requires N . In this case, (j + j

) = x
j
+ x
j
and (j j

) = x
j
x
j
, and therefore both (j + j

) and
(j +j

) remain nite.
Computational Problem 15 (Due November 16, 2008):
15.1 Write a program to solve the time independent Schr odinger equation by using the DVR method and apply it to nd the
rst 10 eigenvalues and eigenfunctions of the Harmonic oscillator introduced by Eq. (10) with m = 1 and = 1. Verify
that the eigenvalues are E() = (1/2 +), = 010.
15.2 Change the potential of the code written in 15.1 to that of a Morse oscillator V ( x) = De(1exp(a( xx
e
)))
2
, with
x
e
= 0, De = 8, and a =
_
k/(2D
e
), where k = m
2
, and recompute the eigenvalues and eigenfunctions.
15.3 Generalize the program developed in 15.1 to solve the 2-dimensional Harmonic oscillator V (x, y) = 1/2m
2
(x
2
+y
2
)
and apply it to nd the rst 10 eigenvalues and eigenfunctions of the Harmonic oscillator introduced by Eq. (10) with m = 1
and = 1. Verify that the eigenvalues are E() = (1 +
1
+
2
).
15.3 Change the potential of the code written in 15.3 to that of a 2-dimensional Morse oscillator V ( x, y) = De(1
exp(a( x x
e
)))
2
+ De(1 exp(a( y x
e
)))
2
, with x
e
= 0, De = 8, and a =
_
k/(2D
e
), where k = m
2
, and
recompute the eigenvalues and eigenfunctions.
36