Basic principles of quantum mechanics, G.

Jeschke, SS 2003

2. Schrödinger equation. Particle in a 1D box

The Schrödinger equation. A Particle in a one-dimensional box
As we have seen, the behavior of quantum particles cannot easily be understood intuitively. It is necessary to use a strict mathematical formulation of the problem at hand, to derive equations for the state of the system and its evolution in time, and to interpret these equations in terms of their physical meaning. This is an elaborate work even for such a simple system as a hydrogen atom. Therefore, we start with an even simpler system- one particle in a one-dimensional box- to obtain a basic understanding how problems are solved in quantum mechanics. In this system we shall already encounter several phenomena such as energy quantization, stationary states, and bound states that are also relevant for atoms and molecules. 1 The wavefunction as a description of a quantum object If we cannot determine the position and momentum of a microscopic object at the same time, we cannot predict its trajectory according to Newtonian mechanics. Clearly, we need a different description of such quantum objects that is different from classical Newtonian mechanics to predict atomic and molecular structures, or in general, the outcome of any experiments on quantum objects. This description will be necessarily abstract, as observations on quantum objects are fundamentally uncertain. The very act of observation interferes with the state of the observed object! This is in conflict with our everyday experience of observing things and processes and with our (naive) view of reality. Thus, we cannot picture quantum objects and we cannot strictly derive the behavior of quantum objects from the known behavior of waves and particles. For this reason we first postulate a few basic principles and examine if the consequences of these postulates agree with experimental facts. Quantum mechanics was developed in this way by in 1925 by Heisenberg (“matrix mechanics”) and 1925/26 by Schrödinger (“wave mechanics”). The two approaches use different mathematics, but provide an equivalent description of quantum objects as was proved rigorously by von Neumann in 1931. In this lecture we restrict ourselves to Schrödinger’s approach, which is more convenient for quantum chemistry. We start with the most simple object we can have. This is a single particle moving in only one dimension along the x coordinate. At time t we characterize the state of this quantum-mechanical system by a wavefunction Ψ. This wavefunction is the quantum-mechanical equivalent

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we can predict the wavefunction at any time in the future by integrating this equation. t )Ψ ( x.2) for finding the particle in the range between x and x + dx . Particle in a 1D box for the characterization of a classical particle by its position and momentum. the particle may have kinetic energy. SS 2003 2. the state with minimum energy for a given time-independent potential V(x). We describe the environment of our system by the potential V ( x. we can only predict a probability.e.e. In other words. The wavefunction in turn provides us with the probability Ψ ( x. by the potential energy of the particle as a function of x and t.. t ) 2 dx (2. in particular. G. t ) . t ) . (2) Give an equation of motion that describes how the state of the system changes with time for a given potential V ( x.Ψ ( x. We usually cannot claim that the particle is at a certain place at a given time. t ) of the system and the left-hand side is the first derivative of the wavefunction with respect to time multplied with a constant. If we know the wave function at time t0. t ) . Schrödinger equation. t ) 2 = Ψ∗ ( x. the wavefunction depends on time and on the coordinates of all particles. Ψ = Ψ ( x. t ) + V ( x.Basic principles of quantum mechanics. Jeschke. t ) . The solutions of these two problems should be given in a form that is useful for physical interpretation. i. where L2 . i.1) This is the time-dependent Schrödinger equation. t ) . 2 The Schrödinger equation determines the wavefunction and its dynamics We postulate the equation of motion as 2 h∂ h -----. t )Ψ ( x. we should have some procedure to predict the outcome of experiments from Ψ ( x. In addition. – -. t ) for our one-dimensional one-particle system. Because of the uncertainty principle. The right-hand side of the equation can be computed from the present state Ψ ( x. Note that for a complex function we have Ψ ( x. The quantum mechanics of this simple system involves only two problems: (1) Determine the possible states and..2 . In general.∂ Ψ ( x. t ) = – 2m ∂ x 2 i ∂t (2.

2m ψ ( x ) d x 2 i f(t )dt (2.3) are ∂ Ψ ( x. since the potential V has dimensions of energy.3) gives 2 ∂t dt ∂x d x2 2 h h2 d– -. By equating the two sides separately to E we obtain two simple differential equations.3) and try to get rid of the time-dependence. (2.------.ψ ( x ) ---. G. To find the possible states Ψ ( x. t ) = f ( t )ψ ( x ) .----------. which we call E . This was postulated by Born shortly after Schrödinger published his equation. t ) for a time-independent potential V ( x ) . SS 2003 2.5) and by dividing by f ( t )ψ ( x ) we obtain h 1 h2 1 d 2 ψ(x) + V(x) .3 . – -.Basic principles of quantum mechanics.6) As the left-hand side (LHS) does not depend on x and the right-hand side (RHS) does not depend on t. From the LHS we find L2 . t ) – -.f ( t ) d ψ ( x ) + V ( x )f ( t )ψ ( x ) dt 2m i d x2 2 2 (2. Jeschke. as we shall see later.d f ( t ) = – -----.4) The product ansatz has the additional advantage that the results can be interpreted more easily. Schrödinger equation.f ( t ) = – -----. This can be done by using a product ansatz for the wavefunction Ψ ( x. Note that the constant has dimensions of energy. t ) = f ( t ) d ψ ( x ) . t ) = – -----2m ∂ x 2 i ∂t (2. Substitution into eqn (2.∂ Ψ ( x. Particle in a 1D box the asterisk denotes the complex conjugate. t ) = d f ( t )ψ ( x ) and ∂ Ψ ( x. The partial derivatives that we need in eqn (2. t ) + V ( x )Ψ ( x. we start from the time-dependent Schrödinger equation which now reads h h2 ∂ 2 Ψ ( x. they must equal a constant.

8) f ( t ) = Ae – iEt ⁄ h .Basic principles of quantum mechanics.11) which is obtained by equating the RHS of eqn (2. Jeschke. Schrödinger equation. (2. (2. The functions ψ ( x ) are solutions of the time-independent Schrödinger equation h2 2 – -----. t ) 2 that characterizes the “distribution” of the particle along the x coordinate at a given time (see eqn (2.12) Ψ ( x. (2. t ) = f ( t )ψ ( x ) . the constant factor A can as well be included in ψ ( x ) .4) as Ψ ( x.= – iE dt . Using eqn (2.2)). The observable of interest in the present problem is the probability density Ψ ( x.4 . G.10) we have ∗ –iEt ⁄ h iEt ⁄ h – iEt ⁄ h ψ( x) ] e ψ( x) = e ψ∗ ( x )e ψ( x) .6) to the constant E and multiplying by ψ(x). ---f( t) h Integration with respect to t yields (2.9) As we are interested in Ψ ( x. 2m d x 2 (2.7) iE ln f ( t ) = – ---. since by making the product ansatz we have possibly excluded other solutions.10) We do not know if all solutions of the time-independent Schrödinger equation have this form. if the potential V does not depend on time there are such solutions and they correspond to states with constant energy E.t + C . SS 2003 2. h where C is the constant of integration.d ψ ( x ) + V ( x )ψ ( x ) = Eψ ( x ) . so that we can write the solution in the form of eqn (2. However. Particle in a 1D box df ( t ) ----------. With the new constant A = e C we obtain (2. t ) = e – iEt ⁄ h ψ(x) . t ) 2 = [ e – iEt ⁄ h = ψ∗ ( x )ψ ( x ) = ψ ( x ) 2 L2 .

G.. Particle in a 1D box This means that the probability density does not depend on time.e.11) simplifies to 1.11) as the Schrödinger equation and to ψ as the wavefunction. must be zero in regions I and III. Boundary conditions result in discrete stationary states. V(x) → ∞ I x=0 II x=l →∞ III x Fig. L2 . SS 2003 2.1 The remaining lectures of this course are concerned solely with the time-independent Schrödinger equation and with stationary states. 3 The Particle in a One-Dimensional Box Before we can see how the Schrödinger equation is solved we have to specify the potential V and the boundary conditions for the wavefunction ψ. only certain values of the energy E are allowed as we shall see in the following treatment of a particle in a one-dimensional box. i. E and ψ. The probability density. For simplicity. The time-dependence corresponds to only a change of the phase of the wavefunction. 2-1). The states of the form of eqn (2. 2-1: Potential energy function V(x) for the particle in an one-dimensional box.Basic principles of quantum mechanics. and hence ψ. it is an inhomogeneous linear differential equation.5 . t ) . not its amplitude. This differential equation is usually subject to boundary conditions for ψ that are related to the physics of the system or its environment. For region II with V = 0 the Schrödinger equation (2. For a given E. as the energy of the particle is finite. Jeschke. The Schrödinger equation has two unknowns. Schrödinger equation. This is sufficient for almost all of quantum chemistry. only in spectroscopy we have to deal with time-dependence of the external potential. This model provides some insight into the UV/vis bands arising from the excitation of electrons distributed over a chain of conjugated bonds with length l.10) are thus stationary states and for many purposes ψ(x) can be used instead of the complete wavefunction Ψ ( x. We shall thus refer to eqn (2. we assume that the potential is zero in the range from x = 0 to x = l and infinite outside this range (Fig.

we obtain sx 2 sx 2m . G.Ee = 0 . (2. Particle in a 1D box h2 d 2 ψ ( x ) = Eψ II ( x ) .18) 2mEx ⁄ h .13) is ψ II = c 1 e with θ = i 2mEx ⁄ h + c2 e – i 2mEx ⁄ h = c1 e + c2 e iθ – iθ . 2 (2. (2.sx s e + -----. we have s + 2mE ⁄ h 2 = 0 .6 . h2 (2. Making this substitution. We see that a linear combination of ψ and its second derivative is zero everywhere. since the derivative of an exponential function is an exponential function times a constant. – -----2m d x 2 II which can also be written as (2. where A and B are constants that have to be determined from the boundary conditions.16) s = ± i 2mE ⁄ h . As e iθ = cos θ + i sin θ . the general solution of eqn (2.13) d ψ II d x2 2 2m + -----. Therefore. This suggests solutions of the form ψ II = e .15) Thus.19) L2 . SS 2003 2.14) This is a linear homogeneous second-order differential equation with constant coefficients. (2. we can also write this as ψ II = A cos [ 2mEx ⁄ h ] + B sin [ 2mEx ⁄ h ] . Schrödinger equation. Jeschke.Basic principles of quantum mechanics.Eψ II = 0 .17) Any linear combination of solutions to a linear homogeneous differential equation is also a solution of this differential equation. 2 h (2.

23) n2h2 E = ----------. i. 3. only n = 1. e. there would be no particle. where n is a natural number. (2.22) As the sine function has zero crossing for arguments ±nπ. Thus.21) We cannot have B = 0 . (2. as this would mean ψ ( x ) ≡ 0 . 2. … are allowed. Hence. By substituting eqn (2.24) in (2. the particle would be missing.21) we obtain the wavefunctions L2 . Jeschke. any nonnegative value of the energy would be allowed. Zero energy. we have boundary conditions ψ ( 0 ) = 0 and ψ ( l ) = 0 . if we require that ψ is continuous. 8ml 2 (2. Schrödinger equation. for instance. A quantum particle cannot be at rest. all other states are excited states.Basic principles of quantum mechanics.20) ψ II ( l ) = B sin [ 2mEl ⁄ h ] = 0 . Particle in a 1D box As ψ is zero in regions I and III.. i. since otherwise both p = 0 and x would be precisely known at the same time. ψ II ( 0 ) = A cos [ 0 ] + B sin [ 0 ] = A = 0 . we find 2 2mEl ⁄ h = ± n . SS 2003 2.7 . which violates the uncertainty relation. In a classical picture (billiard ball between two walls).24) The case E = 0 is special. sin [ 2π 2mEl ⁄ h ] = 0 . would correspond to a ball at rest.. as the wavefunction would again be ψ ≡ 0 . Note that this quantization of the energy is a result of imposing the boundary conditions to ψ. With A = 0 we have for the second boundary condition (2. e. Continuity is a general property of physically reasonable wavefunctions. G. (2. Therefore. The state with lowest energy (n = 1) is the ground state..

ψ ( x ) = 0 elsewhere . -. G. Schrödinger equation.  l  2 0 (2. l l (2.26) Hence. 1. If we settle for a rela positive number. -------. for 0 ≤ x ≤ l .  l  (2. Jeschke. Particle in a 1D box nπx ψ ( x ) = B sin  -------. (2. The uncertainty about the phase is in fact contained in f ( t ) . dx = B 2 -. For the states with n > 1 the wavefunctions feature zero crossings. In fact.25) To fix the constant B. (2. B may be complex.1 the final solution is ψ(x) = 2 sin  nπx for 0 ≤ x ≤ l .Basic principles of quantum mechanics. L2 . More precisely.29) The five lowest energy levels and the wavefunctions corresponding to the three lowest energy levels are shown in Fig. l nπx l B 2 ∫ sin2  -------. which are called nodes. ψ ( x ) = 0 elsewhere . SS 2003 2.27) B = 2⁄l . we use the normalization requirement that the probability to find the particle anywhere in the box must be unity ∞ l l 2 –∞ ∫ ψ dx = 2 ∫ ψII 0 dx = ∫ ψII∗ ψII dx 0 = 1 . 2-2.8 . there are n – 1 nodes where the probability to find the particle vanishes.28) Only the absolute value of B can be determined.= 1 .

31) This is the condition for two wavefunctions ψ i and ψ j being orthogonal.26) to the condition of wavefunctions being orthonormal ∞ –∞ ∫ ψi∗ ψj dx = δ ij .∫ sin  ---------- sin  ---------- dx =  -. L2 . eqn (2. a) Energy levels of the five states with lowest energy.  l π  l   l  l 0 0 l l (2. As sin α sin β = ( 1 ⁄ 2 ) [ cos ( α – β ) – cos ( α + β ) ] .5 nm (5 Å). G. Schrödinger equation. (2. Usually. ∫ sin ( n i τ ) sin ( n j τ ) dx . Another common property of wavefunctions can be recognized by generalizing the normalization integral.Basic principles of quantum mechanics. b) Wavefunctions (bottom row) and probability densities (top row) of the three states with lowest energy. 2-2: Energy levels and wavefunctions for an electron in a one-dimensional box with a length of 0.⋅ -.26). a E (eV) 40 30 b 5 n=1 ×10 9 n=2 n=3 n=5 |ψ| 2 0 n=4 20 6 0 ×10 4 6 0 6 0 6 n=3 10 0 ψ 0 -6 0 r (Å) 6 0 r (Å) 6 0 r (Å) 6 n=2 n=1 Fig. Particle in a 1D box . (2.ψ i∗ ψ j dx = -.30) where τ = πx ⁄ l . SS 2003 2. this is combined with eqn (2. Jeschke. we find ∞ –∞ ∫ ψi∗ ψj dx = 0.9 . to the overlap integral of two different wavefunctions ∞ –∞ ∫ n i πx n j πx 2 2 l .32) where δ ij is the Kronecker delta with is zero (0) for i ≠ j and unity (1) for i = j . i≠j .

Tunneling. there should also be a certain probability to find the electron in allowed region II. Jeschke. In classical physics. 2-4). eqn (1. it would be forbidden that a particle can be found in a region of space where its potential energy is higher than the total energy. In the following. a) Potential energy. Assume that you want to contain an electron in a box with walls of finite height and thickness (Fig.10 . a b c Fig. we consider the somewhat more realistic situation where the walls of the box have finite height (Fig. In particular. The same phenomenon occurs for electrons of an atom or molecule if they are excited to energies that are higher than the ionization energy. Adapted from Levine. In this case the wavefunction does not approach zero for x → ∞ and x → – ∞ and thus cannot be normalized. the wavefunction for the case of a rectangular box with walls of finite height (Fig. You place the electron in the allowed region I. There are also unbound states where the energy is higher than the height of the wall.Basic principles of quantum mechanics. 2-3: Particle in a one-dimensional rectangular well. Quantum Chemistry. G. 2-3). Particle in a 1D box 4 The Particle in a Rectangular Well. This means that the electron has escaped its containment! Quantum-mechanical computations of this problem and of similar problems show indeed that a quantum object can cross L2 . We notice that the wavefunction of the ground state and the first excited state now extend outside the well into the wall. 2-3) leads you to suspect that the electron can penetrate into the forbidden regions.4). These electrons than become free electrons. However. Schrödinger equation. E > V 0 . The mathematical treatment is omitted. The fact that a particle can penetrate into a region of space that would be classically forbidden gives rise to the quantum phenomenon of tunneling. b) Ground-state wave function. c) First excited-state wavefunction. SS 2003 2. Still the wavefunctions and probability densities of the ground state and first excited state approach zero for x → ∞ and x → – ∞ . it can be found in Levine’s book. That a quantum object can be found in such a region is a direct consequence of the uncertainty relation for energy and time. This is despite the fact that the energy of these two states is lower than the height of the wall. Such states are called bound states.

Basic principles of quantum mechanics. Schrödinger equation. Such quantum tunneling becomes increasingly important for objects with decreasing classical behavior. 2-4: Potential energy and classically allowed and forbidden regions for a particle in a one-dimensional box of finite height and thickness. Jeschke. i. SS 2003 2. forbidden V0 allowed I forbidden allowed II Fig.e. tunneling of electrons between the tip of a metal wire and the surface of an electrically conducting sample is used for imaging the surface of the sample in the scanning tunneling microscope (STM). Finally. L2 . Tunneling also contributes to the rate of reactions where hydrogen atoms are transferred.11 . Particle in a 1D box an energy barrier even if its energy is lower than the barrier height. Chemically relevant examples of tunneling are the inversion of the pyramidal structure of an NH3 molecule and the rotation of methyl groups at low temperatures. with decreasing mass of the particles involved.. G.

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