Hydrogen Atom

Bryan Harter, Michael Seigers 29 April 2011

Introduction
Quantum Mechanics is the the study of the behavior and interactions of small particles. Numerical analysis is used extensively in the eld of Quantum Mechanics for modeling interactions of particles and atomic structures as often, there is no analytical solution for a problem. Quantum mechanical systems are described by a wavefunction . The time independent Schrodinger Equation (1), is the partial dierential equation (PDE) used to describe the behavior of the wavefunction of a system where V is the function describing the potential energy of the system and E is the the total energy of the system.
2

2me

2 + V (r) = E

(1)

The classical wave equation is similar to the Schrodinger Equation, however, the E term constrains the system to specic energies. One application of Schrodinger Equation is modeling shapes, locations, and energies of electron orbitals of an atom. The orbital structure of the hydrogen atom is unique in that a reasonably accurate analytic solution exists for it, providing a baseline against which a numerical method can be tested. This project will attempt to model the orbitals of the Hydrogen atom using a numerical nite dierence algorithm. The use of this numerical method will also be used to demonstrate how the quantum numbers used to dene electron states are determined.

Separation of Variables
In the case of the hydrogen atom, V(r) is the given by Coulombs law: V (r) =
2 ke qe r

Because the potential is only dependent on the radius, the best coordinate system to work in will be spherical. We can go about solving this equation starting with the separation 1

of variables technique, where we split into three dierent independent functions of r, , and . (r, , ) = R(r)P()F() Plugging this into equation (1) and expanding 2 , we get the following: 1 d dR 2mr 2 PF 1 2 PF 1 1 ((r 2 ) ) 2 [V (r) E] + (sin() )+ =0 R dr dr PF sin() sin()2 2 We can separate this into two equations, since the r terms and the angular terms must be equal to a constant: 2me r 2 1 d 2 dR ((r ) ) [V (r) E] = 2 R dr dr PF 1 2 PF 1 1 (sin() )+ = PF sin() sin()2 2 We can further rearrange the second equation: d dP 1 d 2 1 [sin() (sin() )] + sin()2 + =0 P d d F d 2 The terms depending on and those depending on must also be equal to a constant, which we will call . Therefore, we get a system of 3 ordinary dierential equations, each depending on a separate coordinate. We note that by rearranging these equations, we can turn all 3 of them into eigenvalue problems: r2 dR 2mr 2 d 2R [ 2 V (r) ]R = ER + 2r dr dr 2 d 2 P cos() dP P = P + 2 sin d sin2 () d d 2F = F d 2 (2) (3) (4)

The remainder of the project will be devoted to solving these three equations. We will approximate the derivatives in these ODEs using the nite dierence method, and create a matrix of values. By solving for the eigenvalues and eigenvectors of these matrices, we can determine the values of the separation constants and , as well as the energy of the system E. Then, by multiplying our allowed solutions together (given by the eigenvectors), we can determine the solution . In order to solve for the allowed energy values, we must rst know what values of we are allowed to plug in to equation (2). This in turn depends on what values of we are allowed to use in equation (3). Therefore, it makes sense to start our search for the solution with equation (4).

Azimuthal Solution
d 2F = F d 2

This equation is not a particularly hard one to solve analytically, however it provides us an opportunity to verify that our nite dierence method works. We approximated the second derivative with d 2 F( i ) F( i1 ) + F( i+1 ) 2F( i ) d 2 h2 where h is the step size. We chose to solve for 300 points between 0 and 2, so the step size was
2 300 .

Because we will have a system of linear equations for each i, we can create a

300x300 matrix. This function is subject to the boundary condition F() = F( + 2k) where k is any integer. By solving for the eigenvalues of this matrix, we obtain the allowed values of . The rst several eigenvalues are given in Table 1. Table 1: The allowed values of alpha from the nite dierence algorithm 1 3.9998896 8.9993376 15.997792 24.994481

When solved analytically, we get that the solution is a sum of sines and cosines, with taking on values of perfect squares. Often, therefore, is written as m2 where m is any integer (positive of negative). We can see that our values of are accurate to within a reasonable degree, so there is no reason as of yet to doubt the nite dierence method.

Co-Latitude Solution
d 2 P cos() dP + P = P 2 sin d sin2 () d

Once again we can use a nite dierence scheme with 300 points to set up the ODE into a system of equations with eigenvalues . We can approximate the derivatives as: dP(i ) P(i+1 ) P(i1 ) d 2h d 2 P(i ) P(i+1 ) + P(i1 ) 2P(i ) d 2 h2 Where h is the step size
300 .

In order to determine the boundary conditions, we must rst assume that > 0, and then multiply the equation above by sin2 (). When we then plug in values = 0 and = (the boundaries), we get the boundary conditions: P(0) = 0 P() = 0

Meaning the values of P(0 ) and P(301 ) are both zero in the algorithm. In this case, we can solve for the eigenvalues and eigenvectors. A table of the rst few allowed eigenvalues can be seen in Table 2 Table 2: Allowed values of from the nite dierence algorithm when = 1 1.999999 5.999889 11.99931 19.99767 29.99418

The solutions to this ODE are well known to be the associated Legendre functions Plm (cos()). The values of in this case are allowed to be of the form l(l + 1) where l is an integer that is = |m|. We can see from our solutions that our allowed values of match the known allowed values very closely. A graph of the rst few eigenfunctions with = 1 are included in gure 1. The case of = 0 If = 0, the boundary conditions are not as clear. We can see from equation (3) that we require that P(0) 0 and P() 0. Unfortunately, we cannot be more specic than this.
dP(0) d

We can, however, rearrange the equation and determine that

= 0. If we say P(0) = 1

for convenience, we can use RK4 to determine the values of the function. Altering the 4

The function P when m = 1 0.1 0.08 0.06 0.04 0.02 0 0.02 0.04 0.06 0.08 0.1 0 0.5 1 1.5 2 2.5 3 P l=1 l=2 l=3

Figure 1: The eigenvectors for = 1 and = 2, 6 and 12 .

boundary value only alters the amplitude of the curve, and does not change the shape. Since we are normalizing the equation anyway, the boundary value is arbitrary. We need to know the allowed values of in advance, however, so this method will only tell us the shape of the eigenvectors, not the allowed values of . The functions are plotted for the rst few values of in gure 2.

Radial Solution
d 2R dR 2me r 2 [ 2 V (r) ]R = ER + 2r dr dr 2 With the values of and in hand, we can solve for the allowed energy eigenvalues and r2 eigenvectors. First o, we should make the substitution u(r) = rR(r) In order to simplify the equation into
2 d2 ke 2 u(r) + u(r) = Eu(r) u(r) + 2me dr 2 r 2m r 2

(5)

Using the technique we used in the last two sections, we can approximate the derivatives as dR(ri ) R(ri+1 ) R(ri1 ) dr 2h 5

The function P when m = 0 1 0.8 0.6 0.4 0.2 0 0.2 0.4 0.6 0.8 1 0 0.5 1 1.5 2 2.5 3 P l=1 l=2 l=3

Figure 2: The eigenvectors for = 0 and = 2, 6 and 12 . d 2 R(ri ) R(ri+1 ) + R(ri1 ) 2P(ri ) dr 2 h2 in order to create a linear system. The boundary conditions are u(r) = 0 u() = 0

which we can see from equation (5), as well as knowing that the wavefunction must go to zero at innity, otherwise the state is not normalizable and therefore does not correspond to a physical solution. The boundary condition at innity provides an interesting challenge to approximate numerically. We set a point far away from the major patterns of the electron and called that point innity. The same value of innity cannot be used every time and still provide accurate results though. For a value of zero, we set our value of innity to be 1.59109 meters. While a larger innity allows us to better approximate states with higher energies, the step size becomes too large compared to the variability of the function for the lowest values of energy, and thus the approximation becomes worse for the lowest values and better for the higher ones. Setting up the equation as an eigenvalues problem, once again using 300 points, we can solve for the rst few values of the energies allowed. Some of these values can be seen in gure 3. The actual observed values of the energy are 13.6 eV, where n is an integer which repren2 sents the energy, and is generally called the principle quantum state of the electron. We 6

Table 3: Allowed values of E from the nite dierence algorithm when = 0, using a maximum radius of 1.59 109 meters Energy (electron volts) -13.571131 -3.3992239084794 -1.50770464318919 -0.670213835921455

12

x 10

18

Radial Wavefunctions n = 0, l = 0 n = 1, l = 1 n = 1, l = 0

10

u(r)2

10

15 r/a0

20

25

30

Figure 3: The eigenvectors u(r) squared for a few dierent values of n and l .

can see that our values come to within a reasonable degree of accuracy. However, depending on which state we are trying to plot, we often found ourselves adjusting the value of innity.

z/a0

3 3

0 x/a0

Figure 4: Contour plot of n=1, l=0, m=0

Wavefunction
We are almost in a position to determine the value of the wavefunction at all points in space. Our last step is to normalize the function squared, meaning we must require ||2 r 2 sin()drdd = 1 since the probability of nding the particle anywhere in space must be 100%. To normalize, we divided the integral into single integrals of each of the three parts coordinates, and integrated each of them seperately using a Simpsons 3/8th integration algorithm. We had to do this for each calculation of the energy eigenstates, as each state was o by a different coecient. Now, for any of the allows values we want of , , and E (or m,l, and n), we can calculate the value of ||2 for any point in space. Because it is dicult to represent this probability density function, we chose to make surface and contour plots of the density function at a value = 0. This shows some of the more interesting structures that arise from the dierent values. The value a0 labeled on the below graphs is the Bohr radius, which is 5.3 1011 meters. The axes, then, are in units of Bohr radii.

Figure 5: Surface plot of n=1, l=0, m=0

500

400

300

200

100

z/a0

100

200

300

400

500 500

400

300

200

100

0 x/a0

100

200

300

400

500

Figure 6: Contour plot of n=20, l=19, m=1. Note how far away the major features of this wavefunction are from the size of the 1s state

Table 4: Surface plots of wavefunctions with nlm values 310,320,321,and 420

Conclusions
This project developed a model capable of computing the electron orbitals for any allowable set of hydrogen quantum numbers. The use of spherical coordinates also demonstrates how the quantum numbers are derived from the eigenvalue equation for each dimension. The model from this project is able to accurate approximations for the Energy levels of each orbital, as well as the allowed values of the magnetic and principle quantum numbers. The accuracy of the numeric model depends on specifying a high resolution over the domain in which the orbitals exist. Follow up work for this project would include writing code to display full 3D surface contours for orbitals. A more generalized model could also be created for application to any atom. Also, implementing a numeric method that employs variable step size could save computation time by allowing for small steps where 2 is steep and larger steps when 2 is at.

10

20 10 15 10 5 5 z/a0 0 z/a0 10 5 0 x/a0 5 10 0 5 5 10 15 10 20 20 10 0 x/a0 10 20

15

25 20

10

15 10 5

z/a0

z/a0 10 5 0 x/a0 5 10 15

0 5

10 15 20

10

15 15

25

20

10

0 x/a0

10

20

Table 5: The contour plots of the 3D plots in Figure

References
1. CSERD: Angular Solution of Hydrogen Lesson Shodor: A National Resource for Computational Science Education. Web. 27 Apr. 2011. <http://www.shodor.org/refdesk/Resources/Activities/AngularHydrogen/>. 2. Griths, David J. Introduction to Quantum Mechanics. Upper Saddle River, NJ: Pearson Prentice Hall, 2005. Print. 3. Schrodinger Equation Concepts Test Page for Apache Installation. Web. 27 Apr. 2011. <http://hyperphysics.phy-astr.gsu.edu/hbase/quantum/schrcn.html>.

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