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Lecture 14.

Hydrogen Atom
Atom is a 3D object, and the electron motion is three-dimensional. We’ll start with the
simplest case - a hydrogen atom. An electron and a proton (nucleus) are bound by the
central-symmetric Coulomb interaction. Because mp>>me, we neglect the proton motion (the
reduced mass is very close to me, the center of mass of this system is ~2000 times closer to
the proton than to the electron). Thus, we can treat this problem as the motion of an
electron in the 3D central-symmetric Coulomb potential.
Three dimensions – we expect that the motion will
be characterized with three quantum numbers (in
fact, there will be the fourth one, the electron spin,
which corresponds to the “internal degree of
freedom” for an electron; the spin will be added later
“by hand”, it is not described by the non-relativistic
quantum mechanics).

e2
U U  r  
4 0 r

E < 0 – bound motion, discrete spectrum,
E > 0 – unbound motion, continuous spectrum

The task: solve the t-independent S.Eq. for E<0, find the energy eigenvalues (the
spectrum) and eigenfunctions (stationary states).

and the angular momentum r about the center is conserved: r r is antiparallel to F  This makes L especially useful for analyzing the central force motion. in our Figure. the electron and the coordinate origin.Orbital Motion in Classical Mechanics r r r v We consider the case of a central force: the force is directed along the line that connects the electron and proton or.  . a non-zero torque leads to the time dependence of L:   r dt r r r dL r dp r In the field of a central force. the torque    r   rF 0 dt dt is zero. Coulomb interaction is responsible for acceleration: r F  e2 r mv 2 r r  2 r 3 4 0 r r  mv 2  F  r   2 2 mv p Kinetic K   energy: 2 2m p   2 r  pt2  2m pr and pt – the radial and tangential components of the momentum r r r The angular momentum L  r  p p  K 2 r  pt2  2m r r r r r r r r L  r  p  r   pr  pt   r  pt pr2 L2   2m 2mr 2 For a circular motion: L2 K 2mr 2 r r dL In general.

z    x. t  t h d d d h pˆ        i  dx dy dz i 2 2 2 2   h d d d ˆ H   2  2  U ( x. y . t     x. z .Quantum-Mechanical Approach As usual. t  t 2 2 2 h2     x. we start with the time-dependent Schrödinger Equation (but now it is 3D case): ih   x. z   E  x. Eigenfunctions correspond to the stationary states with a well-defined energy. Eq. y . z . y . thus we can separate time and space variables: dT  t  ih  ET  t  dt Hˆ   x.solution of the t-independent S. t     x. y. z. y. z . z   iEt   h   x. t  ih  Hˆ   x. t    E  x  exp  . y . . y. gives us the eigenfunctions (the orthogonal basis  i) and eigenvalues (spectrum Ei) of the Hamiltonian.potential energy of Coulomb interaction between electron and proton Laplacian 2   x. z . z    e2 4 0 e2  2 2 2 4 0 r x y z . y. z )  2 2m  dx dy dz  K operator U operator The potential is time-independent. y. t        U  x. y. t  2m  x 2 y 2 z 2  U  x.

Spherical Polar Coordinates The Coulomb potential has central symmetry (U(r) depends on neither  nor  ).a (small) volume element used for integration (no relation to the torque ) . It’s to our advantage to use spherical polar coordinates (this will allow us to separate variables). r x y z 2   cos 1 2 .azimuth angle .distance from origin to point P 2 z x y z 2 2   tan 1 y x 2 .zenith angle .

   0 h After multiplying by r2sin2    sin   r 2   sin  r  r 2     2 2m 2 2  e2  sin    2  2 r sin   E    0     h 4  r 0  . y. . z    x. z    2 2 x y z 2   r . y. . y. z   E  x.   1   2   r .   1  1  2 2 r   2  sin   2 r r  r  r sin     r sin   2 2m  2  E  U  r .t-independent Schrödinger Equation in Polar Coordinates 2 2 2 h2     x. z   2  x.  . z . y . y . y.  . z   2  x.  . z  2 2 2 2m  x y z   2  x. z . t        U  x.    2  r . y. y. y. z     x.     r . t     x.

   R  r          d d  1 d 2  2m 2 2  e2  sin     2 r sin   E   0 2  d d   d h 4 0 r  To show that the variables are separable. one can separate the variables by using a trial function sin 2  d  2 dR sin  r  R dr  dr    r . . let’s rewrite: sin 2  d  2 dR sin  r  R dr  dr  d d  2m 2 2  e2  1 d 2 sin    2 r sin   E    2 d d  h 4  r  d  0  Since the left and right sides depends on different variables. both parts should be equal to the same constant: Divide by sin2 and regroup: 1 d 2 2   m l  d 2 ml2 1 d  2 dR 2m 2  e2  1 d d  r  r E    sin    R dr  dr h2  4 0 r sin 2   sin  d d  .Separation of Variables    sin   r 2   sin  r  r 2     2 2m 2 2  e2  sin    2  2 r sin   E    0      h 4 0 r  For a spherically-symmetric potentials (U =U(r)).

in a more conventional form: Equation for ()  2m  l  l  1 1 d  2 dR e2  r  2  E R0  2  r 2 dr  dr h 4  r r 0      ml2  1 d   sin     l  l  1  2    0  sin  d   sin   d 2 2  m 0 l 2  .Separation of Variables (cont’d) Thus 1 d  2 dR 2m 2  e2  r   2 r  E   l  l  1  R dr  dr h 4 0 r  Equation for R(r) ml2 1 d    sin   l  l  1 2   sin   sin  d   Equation for () 1 d 2 2   m l   2 Or.

.to be discussed in more detail at Lz  hml Discrete eigenvalues of the angular momentum along z axis: the next lecture solution provided l  ml . thus Aei ml   Aei ml    2  ml must be integer ml – the magnetic quantum number What is the range of ml variations?  ml2  1 d   sin     l  l  1  2    0  sin  d   sin   Thus.. .the angular momentum along this axis is the “generator” of rotation around this axis The wavefunction must be single-valued..this Eq. l h Lˆz   Aeiml  hml  i ... 2.Azimuth Part of the Eigenfunctions d 2 2  m l 0 2  h  Lˆz  i  Lˆ2z   h2 ml2   Aei ml  . has a solution provided ml  0. 1...

Equation for the Radial Part R(r)  2m  l  l  1 1 d  2 R e2  r   2  E R0  2 2   r dr  r 4 0 r r   h  h2l  l  1  d 2 R 2 dR 2m    2  E U  r   R0 2 2  dr r dr h  2mr  2 2 2 h l  l  1   h d 2 d Hˆ r     U  r  2  2 2m  dr r dr 2mr pr2 L2 Kr  K 2m 2mr 2 Note that only this equation includes the total energy. being expressed as the “radial” portion of the Hamiltonian What is the structure of this Hamiltonian? Recall that in classical mechanics L2 Er  K  U  r  2mr 2 L2  h2l  l  1 Hˆ r R  r   ER  r  1  2 L2 K  pr  2 2m  r .the eigenvalues 2 of the operator Lˆ this term corresponds to the kinetic energy of the “radial” motion (total kinetic energy minus the kinetic energy of tangential motion) . or.

Equation for the Radial Part R(r) (cont’d)  2m  l  l  1 1 d  2 R e2  r   2  E R0  2 2   r dr  r 4 0 r r   h  d 2   r  2m  h2l  l  1  e2  2  E    r  0 2 2 2  dr h  4 0 r 2mr  substitute   r R r  r formally. and.ml     ml     ml Rnl  r  l .ml  HR nl l .ml     ml    Lˆz n . t   Rn .  should 0 at r=0 (also at r)  n . R should be finite as well.  .ml  Lˆz Rnl  r  l .l  r  l .ml     ml    . ml ml Lˆ2 n .Eq. thus. for 1D motion in the potential h2l  l  1 e2 U  r   2 2mr 4 0 r 2 If U(r) is everywhere finite.l .l . . this equation coincides with the S.ml     ml    e  iEnt ˆ  r       E R  r      Hˆ  n . ml ml n nl l .l .l .ml  Lˆ2 Rnl  r  l .ml  r .ml     ml     l  l  1 Rnl  r  l .

2... l  0.... 3.... 1.  n  1 ml  0.    R  r          R  r   depends on n and l      depends on l and ml      depends on ml n  1.. 2. . solutions exist if ... 1. 3... for the bound states in H atom:   r .. me 4  1 E1 En      32 2 02 h2  n 2 n2 and The latter requirement can be expressed as a condition on l n  1.... 2....Quantization and Eigenfunctions  2m  l  l  1 1 d  2 dR e2  r   2  E R0  2 2   r dr  dr 4 0 r r   h  For the bound motion. 2. 2.. t   R  r          e  iEnt   r .... n  l 1 l  0. l .  ... . 1.the spectrum of this equation is continuous for E>0 (unbound motion) and discrete for E<0 (bound motion).  n  1 Thus..

the energy of the electron in H atom does NOT depend on its angular momentum! Different eigenfunctions with the same n but different l must have the same eigenvalue of Hamiltonian (the electron total energy). the degeneracy is a consequence of the 1/r potential.Degeneracy: Feature of 1/r Potential E1 me 4  1 En      32 2 02h2  n 2 n2 n  1.the motion along these two orbits with the same 2a and different values of L would correspond to the same total energy This degeneracy shows up in quantum mechanics in that one finds the same eigenvalue of Hamiltonian for several different values of the angular momentum quantum number. For the electron states in H atom. 3... they are said to be degenerate. . and there is also a degeneracy: the energy of the bound states depends only on the semi-major axis of the ellipse and NOT on the angular momentum 2a e2 1 E 4 0 2a . bound states in a 1/r potential are ellipses.. In Newtonian mechanics. 2. . Degeneracy: if two or more (distinct) quantum states have the same energy.

me 4 E1    13... 3..Electron Spectrum me 4  1 E1 En      32 2 02 h2  n 2 n2 n  1. 2.6eV 2 2 2 32  0 h .

t   Rn 1.053nm 0 me . l = 0.0  r . ml = 0) d 2 R 2 dR 2m   2  E  U  r  R  0 2 dr r dr h For all s-states (l=0).7):  2 P  r  dr  R r dr   sin  d   d  R r 2 dr 2 2 0 2 2 0 r2dr captures the volume of the shell 2 .Ground State (n = 1. the angular momentum is zero. ml = 0): 1.l 0  r  l 0. l = 0.0.l 0  r  1  r / a0  iE1t  e e 3/2  a0 4 0 h2 .the Bohr radius o a0  2 a  0.ml 0     ml 0    e  iE1t Rn 1.  . and the radial equation is reduces to The ground state (n = 1.recall that we got this estimate from the uncertainty principle P  r  d  R d 2 P r  2 R r2 d  r 2 sin  drd d The probability of finding an electron in a spherical shell between r and r+dr from the nucleus (§6.53A=0.  .

. 3. 2. r3s = 10 Å .Other l = 0 States (s-states) For all s-states. the angular momentum is zero: n  1. r2s = 3.. l  0 ml  0 n=2 n=3 “Boundary” sphere: r1s = 1.3 Å.4 Å..

3 . l  0 2 s p d 1 l =1 – p state l =2 – d state 2 etc. Eigenfunctions for n  2.

2..Comparison with Bohr’s Model (Beiser § 4...g. 3. Combining these two equation. Below we consider this model using de Broglie terminology: an electron can circle a nucleus only if its orbit contains an integer number of de Broglie wavelengths. we get the correct formula for the energy eigenvalues (one of the most successful wild guesses ever made) This model has a huge historical importance. The difference between the probability to find an electron at some distance r from the nucleus according to Bohr model and that in the quantum model is dramatic at lower n: e. n  2 rn h h 4 0 r   p e m e2 e2 e2 En  K  U    8 0 rn 4 0 rn 8 0 rn E1 me 4  1 En      32 2 02h2  n 2 n2 n  1. 3.4) Niels Bohr (1913) (a decade before de Broglie’s work !) proposed the first successful semi-classical model of an atom: circular electron motion as a standing wave.. but because of its semi-classic nature (orbits. according to quantum mechanics the angular momentum is 0.. it is a poor and misleading picture of what is really going on in H atom.. and the probability peaks at the nucleus position! . n 2 h 2 0 2 rn   n r1 2  me n  1.).. etc. at n=0 (the ground state). 2.

! 2. and the average value of 1/r for a 1s electron is exactly 1/a0. though in the quantum model the electron on average is farther away from the nucleus. Find the average value of 1/r for a 1s electron in H atom. However.functions R. . .  are normalized separately!   r3 0  2 3   2r  2 r  2r a0  2 r  4 1 1 exp  dr sin  d  d   exp         d  3   a0 2 2 4  0  a0   a0  a 0  a0  0 1 1  n x x  e dx  n ! r 1s 0  a0 3 3!  a0 4 2 At first glance. the Coulomb potential energy depends upon 1/r. 1 r  1s   2r  2 r  2r 4 1  2 r  1   r 3 exp    dr    exp   d   a0 a0  0  a0  a0  a0  a 0  a0 0 At home: Calculate the mean value of the potential energy experienced by an electron in the 1s-state of the hydrogen atom.1 .Problems 1. r 1s    1*s r 1s r 2 sin  drd d   Table 6. Find the average distance of a 1s electron from the nucleus in H atom. it’s puzzling: the energy levels are the same in both quantum and Bohr atom models. Show that the average kinetic energy is equal to the total energy with its sign changed.

Problems 3. l =1. ml=-1 : Construct   r.   r. l =1. t      r .0   1 1 3 1 r  r /2 a0 iE2t  ei e  i  sin   e e  3/2 2 2 2 2 6a0 a0 1 1 r  3/2 e  r /2 a0 sin  cos  e iE2t 4 2 a0 a0 the rest – at home 1   211  211  2 . 2  Pr1sa0 x e 2 x dx  e   2r  2 r  2r 1  2 r  2 4   r 3 exp    dr    exp   d  a0 2  a0  a0   a0  a 0  a0 a0 x x 2  2x  2  1s r  a0 P 1 1   x 2 exp   x  dx  e 2  22  2 2 2  0. A hydrogen atom starts out in the following linear combination of the stationary states n=2.68 22 2 3. Calculate the probability to find an electron in the 1s-state outside the first Bohr orbit. ml=1 and n=2. t  and find the expectation value of the potential energy.