Notes on Quantum Mechanics

Salvatore Cardamone, 2014

1

Pre-requisites

1.1

Plane Waves

Consider a single-dimensional sinusoid moving along the x-axis with amplitude A0 . The
magnitude of the wave at position x and time t is given by the function
A(x, t) = A0 cos(kx − ωt + φ)

(1)

where
• k is the wavenumber, and is equal to 2π/λ, λ being the wavelength of the wave.
k has units of radians per unit distance, an so corresponds to the rate at which
A(x, t) changes over a given distance.
• ω is the wave’s angular frequency, and is equal to 2π/T , T being the period of
the wave. T has units of radians per unit time, and so corresponds to the rate at
which A(x, t) changes over a given length of time.
• φ is the phase of the wave, which corresponds to a shift of the wave along the
direction of propagation.
This formalism is easily generalised to a wave moving in a higher dimensional space by
treating the direction and wavenumber as vectors, termed a plane wave, such that
A(r, t) = A0 cos(k · r − ωt + φ)

(2)

where r is now a position vector corresponding to a point in R3 , and k is the wave vector.
Each component thus maps the rate at which A(r, t) changes over a given displacement
along the corresponding basis vector. The direction of the wave vector is typically in

1

However. Mathematical manipulation of planes waves is greatly facilitated by use of the complex exponential form.e. in the bulk of this document. we are left with the trivial operation of taking the real quantity of U (r. Multiplying each side by the complex conjugate of our exponential (introducting the dummy variable p) and integrating over a single period of f (x). solutions to the Schr¨odinger Equation are by their very nature complex. termed a Fourier Series. trigonometric functions). such that U (r. t) = A(r. between x0 and x0 + L 2 . expanding our function f (x) = ∞ X cn eikn x (4) n=−∞ where kn = 2πn/L.2 1.1 Fourier Analysis The Fourier Series Consider a function. t)) = A(r. the plane wave is a real entity and we have generated a function which is complex. which is periodic with period L. but is in fact an inherent part of the wave. f (x). it may be expanded in a series of imaginary exponentials (and thus. t) = A0 ei(k·r−ωt+φ) = A0 eiφ ei(k·r−ωt) = U0 ei(k·r−ωt) Obviously. i. t) = A0 cos(k · r − ωt + φ) As a final word on the topic. t) <(U (r. and so the imaginary component in this occurrence has not been introduced as a byproduct. once we have performed our calculations in the complex plane.2. 1.the direction of propagation of the plane wave. We proceed initially with the complex exponential form. t) = A0 cos(k · r − ωt + φ) + iA0 sin(k · r − ωt + φ) U (r. t) + iA0 sin(k · r − ωt + φ) This form is simplified somewhat by modifying the amplitude of the wave to absorb the phase factor. whereby the plane wave is described by U (r. If f (x) obeys certain mathematical conditions. t) = A0 ei(k·r−ωt+φ) (3) Expanding this in terms of sines and cosines U (r.

the Fourier coefficients of which are cn and dn . Such a relationship proves to be extremely useful if we consider the scenario where we have two functions. δpk .2 Z 1 L x0 +L f (x)e−ikn x dx (5) x0 The Bessel-Parseval Relation From (4). respectively. f (x) and g(x). and realisation that the integral of the constituent sinusoids over the period is equal to zero. L. then the right hand side simply becomes x0 +L Z dx = L x0 allowing us to elegantly conclude that Z x0 +L ∞ X f (x)e−ikp x dx = x0 an Lδnp = ap L n=−∞ where we have introduced the Kronecker delta. we may obtain x0 +L Z |f (x)|2 dx = x0 Z x0 +L f ∗ (x)f (x)dx = x0 x0 +L x0 Z |f (x)|2 dx = Z x0 ∞ X ∞ Z X n=−∞ p=−∞ x0 +L ∞ X x0 +L ∞ X c∗p cn e−ikp x eikn x dx n=−∞ p=−∞ c∗p cn ei(kn −kp )x dx = x0 ∞ X ∞ X c∗p cn δnp L n=−∞ p=−∞ where the Kronecker delta arises in a manner equivalent to that shown in the previous section.2.Z x0 +L ∞ X f (x)e−ikp x dx = x0 x0 +L Z cn ei(kn −kp )x dx x0 n=−∞ The integral of the exponential function on the right hand side of the above allows for a significant simplification upon decomposition into the corresponding trigonometric functions. since Z x0 +L  cos x0 2πn 2πp − L L   Z x dx = x0 +L  cos x0 2π(n − p)x L  dx = 0 with the same obviously being true for the sine function. Therefore. However. We may subsequently generalise (6) such that 3 . if n = p. the coefficients of the Fourier Series are given by an = 1. each with the same period. Subsequent simplification leads us to 1 L Z x0 +L |f (x)|2 dx = x0 ∞ X |cn |2 (6) n=−∞ which is termed the Bessel-Parseval Relation.

Consider a function f (x) which is not necessarily periodic. and utilise this in kn+1 − kn = our initial Fourier series. 4 . such that 1 cn = L Z x0 +L e −ikn x x0 1 fL (x)dx = L Z L 2 e−ikn x f (x)dx −L 2 We recall that the various kn were defined by kn = 2πn/L.1 L 1. Also note that in this limit. allowing us to form a recursive relationship 2π 1 kn+1 − kn ∴ = L L 2π which we substitute into our expression for the Fourier coefficients. (kn+1 − kn ) → 0. we establish a function 1 F(k) = √ 2π ∞ Z e−ikx f (x)dx (8) eikx F(k)dk (9) −∞ which may be used to generate 1 f (x) = √ 2π Z ∞ −∞ where f (x) and F(k) are termed the Fourier Transforms of one another.2. such that the summation over n is transformed into a definite integral over the continuous variable k. We define fL (x) to be a periodic function of period L which is equal to f (x) over the interval [−L/2. yielding Z L ∞ X kn+1 − kn ikn x 2 −ikn x e fL (x) = e f (x)dx 2π −L n=−∞ 2 As L → ∞.3 Z x0 +L ∞ X g ∗ (x)f (x)dx = x0 d∗n cn (7) n=−∞ The Fourier Transform We begin this section with the statement that the fourier integral is a limit of a Fourier series. L/2]. Re-establishing the limits of our integral in the above equation to allow for L → ∞. f (x) → fL (x). As we have shown. fL (x) may be expanded as a Fourier series fL (x) = ∞ X cn eikn x n=−∞ where our Fourier coefficients are defined by (5). and so we are essentially approximating our unknow function f (x) by some analytic periodic function fL (x).

t) can be expanded in terms of the eigenfunctions of A ψ(r. t) is interpreted as a probability amplitude of the particle. then a measumrent of A at time t will yield the eigenvalue a. The probability that a particle is a time t in an infinitesimal volume element dr is given by dP (r. The quantum state of a particle is characterised by a wavefunction. t) is the corresponding probability density function.1 Introduction Quantum mechanics divides the world into two parts composed of a system and an observer. ψa (r). t)|2 gives a corresponding probability density. A measurement changes the information an observer has about the system. structureless particle. Neglecting particle destruction/ creation (as occurs with photons in relativistic quantum mechanics). t)d r = 1 Z ∴ |ψ(r. which contains all information regarding a system which an observer can possibly obtain. t) = X a 5 ca ψa (r) (12) . t) = ψa (r). 2. 3. t)|2 dr (10) where C is some normalisation constant and P (r. Applied to a system consisting of a single. often represented in terms of a wavefunction. (c) Any ψ(r. (b) Each eigenvalue is associated with an eigenfunction. t). A. t) = C|ψ(r. The principle of spectral decomposition applies to the measurement of an arbitrary physical quantity.2 Fundamental Assumptions of Quantum Mechanics 2. the particle must occupy some portion of space. such that. If ψ(r. except during the process of measurement. {a}. Quantum mechanics predicts all the information an observer may obtain regarding a system. and therefore changes the wavefunction of the system. 1. ψ(r. and so |ψ(r. t)|d3 r < ∞ R3 (11) where the final statement implies that a wavefunction must be square-integrable. t)| d r C R3 2 3 Z → R3 |ψ(r. which do not interact. the fundamental assumptions of quantum mechanics are. ψ(r. and so we are free to write Z 3 P (r. (a) The result of a measurement belongs to a set of eigenvalues.

t) ∂t ∇ψ(r.The corresponding probability that a measurement at time t will yield the eigenvalue a1 is subsequently given by |ca |2 P (a1 ) = P 1 2 a |ca | (13) which is readily obtained when one implements the fact that the eigenfunctions for a mutually orthonormal basis. t) = ikψ(r. t) = ~2 k 2 ψ(r. t)ψ(r. and so we may arbitrarily set V (r. t) and recombining to form the Schr¨ odinger Equation ~ωψ(r. t) i~ ∂ ~2 2 ψ(r. The Schr¨ odinger Equation describes the evolution of ψ(r. t). t) + V (r. t) = 0. we obtain ω= E= 6 p2 2m (17) (18) . (d) If a measurement of A yields a. t) = − ∇ ψ(r.2 A Free Particle A free particle is not subjected to any forces. t) 2m which constrains our choice of ω to ~k 2 2m By use of the de Broglie relations. t) ∂t 2m (14) where the particle has a mass m and is subjected to the potential V (r. t) = −iωψ(r. t) = −k 2 ψ(r. t) = Aei(k·r−ωt) (15) (16) Finding the various derivatives of this function ∂ ψ(r. 4. of form i~ ψ(r. t) = − ∇ ψ(r. E = ~ω and p = ~k. allowing for subsequent simplification of the Schr¨odinger Equation to ~2 2 ∂ ψ(r. then the wavefunction of the system immediately after measurement is given by ψa (r). t) ∂t 2m Plane waves are potential solutions to the above. 2. t) ∇2 ψ(r.

which is simply the kinetic energy of the particle. that if a set of functions satisfy the equation. i. we take the case of a onedimensional wave packet. then a linear combination of them is also a satisfactory solution. We note that a plane wave represents a particle whose probability distribution is constant throughout space |ψ(r. a linear combination of plane wave solutions is also a solution ψ(r. t) as a Fourier transform Z 1 ψ(r. As such. t)dr = |A| 2 Z ∞ dr = ∞ −∞ −∞ Since the Schr¨ odinger Equation is linear. as we would expect given we assumed no external potential. t) = √ 2π Z ∞ g(k)ei(kx−ωk t) dk −∞ 7 (21) . t) = (2π)3/2 g(k)ei(k·r−ωt) dk (20) R3 Such a wave function is called a three-dimensional wave packet. t)ψ(r. and may represent any square-integrable function. we are free to write ψ(r. t)| |Ae−i(k·r−ωt) Aei(k·r−ωt) | = |A2 | which is not a proper solution to the Schr¨odinger Equation as this is not square-integrable by virtue of Z ∞ ∗ ψ (r. As such. t) = X ak ei(k·r−ωt) (19) k recalling that we have the constraint that ~k 2 2m It is hoped that the reader recognises (19) as being a three-dimensional equivalent to ωk = (4). whose wavefunction is given by 1 ψ(x. t)ψ(r. the principle of superposition applies. For the sake of simplicity. t)|2 = |ψ ∗ (r.e.

i.A Brief Example We may gain some insight regarding the physical form of a wave packet by considering a superposition of a finite number of plane waves. 0)e−ikx dx −∞ We assume g(k) to be some normally distributed function centred at k0 with width ∆k. with wavenumbers k0 . 12 . leading |ψ(x. and find the values of 2 . we see that (21) is periodic in x. We take the interval of    ∆x ∆x  ∆x the wave packet to span x0 − ∆x ≡ − 2 . the more diffuse the function |ψ(x)| becomes (the distance between the two nodes of ψ(x). and only a single maximum exists. + 2 . k0 + 2 Then. In this case. respectively. and amplitudes 1. the three waves which form our wave packet interfere constructively. 0)] = g(k) = √ 2π Z ∞ ψ(x.   ∆k . 0) = √ eik0 x 1 + cos x 2 2π (22) By evaluation of the argument of the cosine. and therefore there exists a series of maxima and minima. 0)| → 0 ∆k when the phase shift between eik0 x and ei(k0 ± 2 )x is ±π.e. At some instance in time. we will take 3. in the limiting case where we take an infinite number of plane waves. we see that the smaller the width. x0 + 2 ∆x and ∆k which satisfy this phase shift condition  k0 + ∆k 2  ∆x k0 ∆x − =π 2 2 k0 ∆x ∆k∆x k0 ∆x + − =π 2 4 2 ∆k∆x = 4π By this. 0) = e + e 2 2 2π    g(k0 ) ∆k ψ(x. ∆x must complement this by increasing to satisfy the above equation. using these in (22). 8 . 0) = √ 2π Z ∞ g(k)eikx dk (23) −∞ 1 F[ψ(x. This is due to the fact that at this value of x. the waves gradually dephase with one another and being interfering destructively. periodicity is lost over the real numbers. we obtain   1 i(k0 + ∆k g(k0 ) ik0 x 1 i(k0 − ∆k x x ) ) 2 2 √ + e ψ(x. k0 − ∆k 2 . 1 ψ(x. ∆k. 0)| is maximal when x = 0. As a point of note. as x moves away from x0 . say t = 0. we see that |ψ(x. of the function |g(k)|. Such a scenario is a result of a superposition of a finite number of plane waves. 12 .

and is given by g(k) = |g(k)|eiα(k) . We further assume that ∆k << k0 . We may expand α(k) in a Taylor series about the point k0 .e. i. .

dα .

.

α(k) = α(k0 ) + (k − k0 ) dk ... + .

leaving us with Z dα 1 ψ(x.k0 We are only interested in the function in a small interval about k0 . 0) = √ |g(k)|eiα(k0 ) ei(k−k0 ) dk eikx dk 2π . and so we discard all second order and higher terms in the above expansion.

.

the integrand barely varies at all. We are now in a position to allude to a particularly important relationship. |ψ(x. 0) = function is the equivalent of a Fourier series. We see that |ψ(x. 0) rapidly become out of phase. and subsequent integration yields |ψ(x. Primarily. when the exponent is equal to one ∆k(x − x0 ) = 1 (which is equivalent to saying the position is equal to the wavelength). which will form the majority of the next section. if x is far-removed from x0 . we wish to reiterate that this ψ(x. Alternatively. Denoting the width of the wave packet by ∆x. 0) = √ |g(k)|eiα(k0 ) ei(k−k0 )(x−x0 ) eik0 x dk 2π Removing the exponentials which are not functions of k from the integral Z ei(α(k0 )+k0 x) √ |g(k)|ei(k−k0 )(x−x0 ) dk 2π which is in a form more amenable to analysis. the waves which form ψ(x. 0). the above reduces to 1 ψ(x. 0) = √ 2π Z 1 |g(k)|eiα(k0 ) e−i(k−k0 )x0 eikx dk = √ 2π Z |g(k)|eiα(k0 ) e−ikx0 eik0 x0 eikx dk Noting that we may add the term eik0 x e−ik0 x to our product of exponentials without altering the function. In other words. and realising that this allows for a factorisation Z 1 ψ(x. and interfere destructively. We initially consider the case where |x − x0 | is large. When x moves away from x0 . Qualitative analysis of this function reveals that the integral over k will then lead to |ψ(x. if x ≈ x0 . i. leading to the integrand oscillating substantially in the interval of ∆k. in which we are essentially taking an infinite number of plane waves to recreate our wavefunction ψ(x. 0)| decreases. Arbitrarily setting x0 = − dα dk k0 . 0)| actually equals zero when the integrand undergoes a single oscillation over the interval ∆k. we see that the above relation gives a lower bound to the exponent 9 . 0)| → 0.e. 0)| tending towards its maximum value.

all values of the momentum are physicall realisable. 0) = √ 1 2π~ Z ipx/~ ¯ ψ(p)e dp and implementing the Bessel-Parseval relation (6). we see that the energy and momentum of the system are well-defined and unrestricted. in that k0 and ω0 may take any real value. we see that 1 |ψ(x. ~(k + dk)] is therefore given by |g(k)|2 dk. and allows us to derive some physical restrictions to what may be known about a system. However. 0) occurs as a linear superposition of momentum eigenfunctions. We may view this in a different manner by spectral decomposition. 0)|2 dx C which is the probability of the particle being found in the interval [x. consider (22). Since k may take any real value. dP (k). x + dx] at t = 0. we obtain Z ∞ |ψ(x. with coefficients g(k). 2. if we have a particle defined by the wavefunction ψ(x. there are an infinite number of eigenvalues which one may realise upon measurement of the state. in which ψ(x. 0)|2 dx = −∞ Z ∞ 2 ¯ |ψ(p)| dp −∞ Denoting the value of the integral to be C. of obtaining an eigenvalue in the interval [~k. Rewriting (22) in terms of the momentum ψ(x.∆x∆k ≥ 1 (24) which is nothing more than a classical relation between the widths of two functions which ae Fourier transforms of one another.3 The Heisenberg Uncertainty Principle The inequality in (23) proves to be extreme importance in quantum mechanics. by use of the de Broglie relations (E = ~ω0 and p = ~k0 ). and so is a probability density for the eigenstates of the system. This allows us to interpret |g(k)|2 as the probability of finding a system in the eigenstate eikx . Given a plane wave of the form ei(k0 x−ω0 t) . as in classical mechanics. dP (x) = In an entirely equivalent manner dP (p) = 1 ¯ |ψ(p)|2 dp C 10 . 0) = Aeikx then in saying the particle has a well-defined momentum p is equivalent to saying that eikx characterises a momentum eigenstate with eigenvalue p = ~k. The probability.

which is the probability of the particle having a momentum in the interval [p. Now. returning to our inequality (23). c. there is nothing inherently quantum mechanical about (24) as it merely expresses a general property of Fourier transforms.. Therefore. Vφ (k). given by ω k We may draw physical insight from this by considering the case of an electromagnetic Vφ (k) = wave. p + dp]. we rewrite ∆x∆p ≥ ~ (25) ¯ where ∆p = ~∆k and represents the width of ψ(p). p0 + 2 . Then.e. numerous examples of which exist within classical physics. n(k). This relation is known as the Heisenberg Uncertainty Relation. we cannot know both the position and the momentum to an arbitrary degree of accuracy. Heisenberg’s Relation does not arise from some strange physical phenomenon. Reiterating what was said in the previous section. it is merely a byproduct of some well-defined mathematics which manifests as some bizarre principle when applying to physical reality. There is no analogous phenomenon within classical mechanics. We may therefore interpret (24) as the impossibility of being able to simultaneously decrease the product of the uncertainties in both the position and the momentum of a particle below ~. the limitation expressed in (24) arises from the fact that ~ is not equal to zero. such that Vφ (k) = c n(k) Recall (17). the phase velocity of a wave is moderated by the index of the medium. As such.4 Time-Evolution of a Wave Packet A plane wave ei(kx−ωt) propagates through space with a Phase Velocity. we cannot simultaneously know the position and wavelength of an electromagnetic wave with infinite accuracy. on the other hand. In a dispersive medium. if one were to measure the i momentum of the particle at the same time. 2. which allows us to write Vφ (k) = ω ~k = k 2m 11 . the phase velocity of which in a vacuum is independent of k and equal to the speed of light. i. so that ∆x represents the uncertainty in our knowledge in the position of the particle. e. consider a particle whose position probability is defined by some region ∆x about x0 . it is only because ~ is extremely small by macroscopic standards that we do not encounter the physical consequences of this inequality on the macroscopic scale.g. the uncertainty in the momentum being given by ∆p. a value in the interval h ∆p ∆p p0 − 2 .

respectively. we see that all three waves will be at their maximum value and so reinforce constructively to give xmax . and dephase as we move along x. thus 1 ψ(x. we have just seen that the phase velocity is dependent upon k. with wavenumbers k0 . However. We begin by attempting to understand a qualitative description of what happens once a wave packet is allowed to evolve with respect to time. angular superposition of three plane waves. We can arrive at the same conclusion based on (??). ω0 − ∆ω and amplitudes 1. k0 + 2   ∆ω 1 1 . Consider the  ∆k . we shall see that the velocity of the maximum point of the wave packet. Then.which we see is similar to the phase velocity of a wave in a dispersive medium. t = 0. k0 − ∆k 2 . . all we need to do is change the distribution g(k) to g(k)e−iω(k)t . t)| is given when the argument of the cosine is equal to zero. 0) to ψ(x. t) = √ ei(k0 x−ω0 t) 1 + cos x− t 2 2 2π Thus. ω + . when ∆k ∆ω x= t 2 2 ∆ω xmax (t) = t (27) ∆k which differs from the value given in (25). owing to their differing angular velocities.. velocities ω0 . When the waves which form a superposition have unequal phase velocities. i. for 0 2 2 2 2 arbitrary t   1 i[(k0 + ∆k g(k0 ) i(k0 x−ω0 t) 1 i[(k0 − ∆k x−(ω0 − ∆ω t] x−(ω0 + ∆ω t] ) ) ) ) 2 2 2 2 e + e ψ(x. the maxima from the three waves which were  initially dephased will gradually become in phase as the k0 + ∆k wave catches up with 2 the other two. t) = √ + e 2 2 2π    g(k0 ) ∆k ∆ω ψ(x. We differentiate this function with respect to k and evaluate at k0 to yield 12 . We see that to go from ψ(x. after a given amount of time. At time x = 0. t). is not given by the average phase velocity ~k0 ω0 = (26) k0 2m as one may expect.e. As such. t) = √ 2π Z ∞ |g(k)|e i(α(k)−ω(k)t) ikx e −∞ 1 dk = √ 2π Z ∞ |g(k)|eiβ(k) eikx dk −∞ where we have simply used the identity β(k) = α(k) − ω(k)t and expressed g(k) in polar form. The three waves will emanate from this point. This deviation from expectation has a physical origin which may be demonstrated by an analysis of the constituent waves. xmax (t). we see that the maximum point of |ψ(x. and so the maximum of the wave ∆k 2 characterised by k0 + will propagate along the x-axis quicker than the other two.

.

.

.

dβ .

.

dα .

.

dω .

.

= − t dk .

k0 dk .

k0 dk .

k0 .

.

Recalling that we earlier defined dα dk k0 = −x0 . and substituting in .

.

.

dω .

.

dω .

.

dα .

.

− t = −x − = x0 + VG (k0 )t 0 dk .

k0 dk .

k0 dk .

k0 where we have defined .

dω .

.

= VG (k0 ) dk .

corresponding to a well-defined position. the velocity is given by v = p0 m. 13 .k0 (28) which we term the Group Velocity. and represents the velocity of the peak of the wave packet. and so it is perfectly reasonable to speak of a well defined particle momentum. uncertainty plays no role due to ~ being negligible at the macroscopic level. In this case. We may readily find the functional form of the group velocity by differentiating (17) with respect to k ~k d ~k 2 = = 2Vφ (k0 ) dk 2m m This relationship proves to be extremely important. p0 . xmax (t). the maximum of the wave packet moves like a particle which obeys the laws of classical physics. as it enable us to recover the classical VG (k0 ) = situation for a free particle. In this case. which is implied by the above formula. In the cases where ∆x and ∆p may both be considered negligible.