Appendix : Separation of variables r Here pe is the linear for Hydrogenic Atom momentum of We consider the electron an electron with

mass r and PM the linear me and the charge - e r momentum of the moving at the position re nucleus. me re eZ eZ M Finally = 4 or 4 o | re RM | RM is the Coulomb - potential between electron and and a nucleus of mass M nucleus and the charge Z moving r at position RM . The total Hamiltonian for such re -e r a system will be given by Z 1 2 1 2 eZ RM H= pe + P 2me 2M M 4 or Appendix : Separation of variables for Hydrogenic Atom

Appendix : Separation of variables for Hydrogenic Atom We have Thus r r 1 2 1 2 eZ re R M r H= pe + P = 2M M 4 o | re RM | 2me dt dt me + M dt r r 1 1 eZ v 2 H = me v 2 + MVM me r RM R e = + 2 4 o | re RM | 2 dt dt me + M dt Or r Thus meM 1 meM2 1 H = me V 2 + v2 vV 2 (me + M)2 2 (me + M)2 M v 2M ve = V v r meM me + M + 1 MV 2 + 1 me v2 + vV 2 2 r v 2 (me + M) me r 2 (me + M) VM = V + v eZ me + M 4 or

Or H= r meM 1 meM2 1 me V 2 + v2 vV 2 (me + M)2 2 (me + M)2 r meM 1 m2M 1 e + MV 2 + v2 + vV 2 2 2 (me + M) 2 (me + M) eZ 4 or

Appendix : Separation of variables for Hydrogenic Atom The Hamiltonian : Such a separation is 1 2 1 2 eZ , however,possible if H= pe + PM 4 o | re RM | we introduce a new 2me 2M set of independent does not have the form of a variables. sum of two one particle Hamiltonians due to the term As the first variable we eZ introduce 4 o | re RM | r v r = RM re which depends on the coordinates of both particles.

Or

re

-e

r Z RM

Thus we will not be able to separate the variables by finding solutions of the form r r r r (re , RM ) = e ( re )M (RM )

H=

1 meM(M + me ) 2 1 eZ (me + M)V 2 + v 2 (me + M)2 4 or 2 1 meM 1 eZ (me + M)V 2 + H= v2 2 (me + M) 4 or 2

Appendix : Separation of variables for Hydrogenic Atom We now have 1 meM 1 eZ H= (me + M)V 2 + v2 2 (me + M) 4 or 2 Total mass MT = me + M

reduced mass = me if M >> me

meM (me + M)

re R

We now have 1 1 eZ H= MT V 2 + v 2 2 4 or 2

r RM

Appendix : Separation of variables for Hydrogenic Atom We can now by simple As the second variable manipulation express we introduce the center re and RM in terms of r of mass R r M r re = R r mere + MRM me + M R= me + M r r me v RM = R + r r re me + M R Thus RM r r We note that we can re R M dr = r dt dt me + M dt change R and r indepen r r v dently of each other. me dr RM R = + They are independent dt dt me + M dt variables

Velocity of center Velocity of relative of mass (motion) motion

Appendix : Separation of variables for Hydrogenic Atom

R MT P Free Particle

Here hT (R) T (R) = Eext T (R) is the equation for a free particle of mass MT h2 2 R T (R) = Eext T (R) 2MT

Appendix : Separation 1 1 eZ H = MT V 2 + v 2 of variables for 2 4 or 2 Hydrogenic Atom We can also write 1 2 1 eZ H= P2 + p 2 4 or 2MT We now go to QM 2 2 2 2 P2 > h 2 ( + + ) = h2R 2 X 2Y 2Z 2 2 2 2 p2 > h 2 ( + + ) = h2r 2x 2 y 2z Thus Hamiltonian , h(r), of particle with coordinate r and h2 h2 2 eZ 2 mass H= R r 2MT 2 4 or moving in eZ (R) = Hamiltonian h = V(r ) Coulomb field 4 or for free particle of mass M
T

Appendix : Separation of variables for Hydrogenic Atom

Appendix : Separation of variables for Hydrogenic Atom On the other hand

z
h(r ) (r ) = Eint (r ) eZ h2 2 { } (r ) = Eint (r ) r 2 4 or is the Hamiltonian of the hydrogen atom

-e r

v y x Z
Central Field

We have h2 2 h2 2 r H= 2MT R 2 eZ 4 or

hT (RT ) = -

h2 2 2MT R

Or : H = hT (RT ) + h(r)
h(r) = -

eZ h2 2 r 2 4 or

Movement of a particle of mass r charge - e at r

and
in a field of a particle with charge Z permanently at the r position r = 0.

so that we now have a Hamiltonian that is a sum of two one - particle Hamiltonians

Appendix : Separation of variables for Hydrogenic Atom

Appendix : Separation of variables for harmonic oscillator and rigid rotor

Thus the Schrdinger equation H(R,r) = E(R,r) becomes

We can thus write (R,r) = T (R) (r )

Or

Consider two balls A and B Case II: Stretch

{hT (R) + h(r )} T (R) (r ) = E T (R) (r )

F= -kr A

r = re+r B

Stretch r = re+r
1 1 h (R) T (R) + h(r ) (r ) = E T (R) T (r )

Both terms on the left must be a constant

Thus with E = Eext + Eint

With masses mA and mB

..and kept together by a string of force constant k

The total Hamiltonian for such a system will be given by

hT (R) T (R) = Eext T (R)

h(r ) (r ) = Eint (r )

H=

1 1 1 P2 + P2 kr 2 2mA A 2mB B 2

Appendix : Separation of variables for harmonic oscillator and rigid rotor

r A R rB r

Introducing again the center of mass and internal coordinates

One can write the Hamiltonian as

H = Htrans + Hrot + Hvib

With eigenfunctions : = trans (R)rot (, ) vib (, ) and eigenvalues (energies) E = Etrans + Erot + Evib
Etrans = 1 h2k 2 2 mA + mB

Translation of A - -B as a whole through its center of mass R

Appendix : Separation of variables for harmonic oscillator and rigid rotor

r A R rB

Introducing again the center of mass and internal coordinates

One can write the Hamiltonian as

H = Htrans + Hrot + Hvib

With eigenfunctions : = trans (R)rot (, ) vib (, ) and eigenvalues (energies) E = Etrans + Erot + Evib
Erot = l(l + 1)h2 2Iin

Rotation around center of mass

l = 0,1, 2..
Iin = moment of inertia

Appendix : Separation of variables for harmonic oscillator and rigid rotor

r A R

r rB

Introducing again the center of mass and internal coordinates

One can write the Hamiltonian as

H = Htrans + Hrot + Hvib

With eigenfunctions : = trans (R)rot (, ) vib (, ) and eigenvalues (energies) E = Etrans + Erot + Evib
1 Evib = ( v + )h 2

Vibration around re

v = 0,1, 2.. mAmB k = reduced mass = mA + mB