Notes on Quantum Mechanics
Total Page:16
File Type:pdf, Size:1020Kb
Notes on Quantum Mechanics Finn Ravndal Institute of Physics University of Oslo, Norway e-mail: [email protected] v.4: December, 2006 2 Contents 1 Linear vector spaces 7 1.1 Realvectorspaces............................... 7 1.2 Rotations ................................... 9 1.3 Liegroups................................... 11 1.4 Changeofbasis ................................ 12 1.5 Complexvectorspaces ............................ 12 1.6 Unitarytransformations . 14 2 Basic quantum mechanics 17 2.1 Braandketvectors.............................. 17 2.2 OperatorsinHilbertspace . 19 2.3 Matrixrepresentations . 20 2.4 Adjointoperations .............................. 21 2.5 Eigenvectors and eigenvalues . ... 22 2.6 Thequantumpostulates ........................... 23 2.7 Ehrenfest’stheorem.............................. 25 2.8 Thetimeevolutionoperator . 25 2.9 Stationarystatesandenergybasis. .... 27 2.10Changeofbasis ................................ 28 2.11 Schr¨odinger and Heisenberg pictures . ...... 29 2.12TheLieformula................................ 31 2.13 Weyl and Cambell-Baker-Hausdorff formulas . ...... 32 3 Discrete quantum systems 35 3.1 Matrixmechanics............................... 35 3.2 Thehydrogenmolecule............................ 36 3 4 CONTENTS 3.3 Thegeneraltwo-statesystem . 38 3.4 Neutrinooscillations . 40 3.5 Reflection invariance and symmetry transformations . ......... 41 3.6 Latticetranslationinvariance . .... 43 3.7 Latticedynamicsandenergybands . .. 45 3.8 Three-dimensional lattices . ... 47 4 Schr¨odinger wave mechanics 51 4.1 Coordinatebasis ............................... 51 4.2 The Dirac δ-function ............................. 52 4.3 Continuous translations and momentum . ... 53 4.4 Operators in the coordinate representation . ....... 55 4.5 Themomentumrepresentation. 58 4.6 Threedimensions ............................... 58 4.7 Thewaveequation .............................. 60 4.8 Algebraic solution of the harmonic oscillator . ........ 61 4.9 Hermitepolynomials ............................. 66 4.10Coherentstates ................................ 67 5 Rotations and spherical symmetry 71 5.1 Cyclicmolecules................................ 71 5.2 Particleonacircle .............................. 73 5.3 Axialsymmetry................................ 74 5.4 Planarharmonicoscillator . .. 76 5.5 Sphericalrotationsandthegenerators . ..... 79 5.6 Quantizationofspin ............................. 83 5.7 Spin-1/2andthePaulimatrices . .. 86 5.8 Orbital angular momentum and spherical harmonics . ....... 89 5.9 Spherical symmetric potentials . .... 93 5.10Thesphericalwell............................... 96 5.11Hydrogenatoms................................ 97 5.12 RotationmatricesandEulerangles . 101 6 Approximation schemes 109 6.1 Thevariationalmethod. 109 CONTENTS 5 6.2 Rayleigh-Ritzscheme. .. .. 112 6.3 Staticperturbations. 113 6.4 Degeneracy ..................................116 6.5 Time-dependent perturbations . 118 6.6 Harmonicperturbations . 121 6.7 Rutherfordscattering. 122 6.8 Quantumpotentialscattering . 125 7 Electromagnetic interactions 129 7.1 Magneticmoments ..............................129 7.2 Vectorpotentialsandgaugeinvariance . 130 7.3 Gaugetransformationsinquantumtheory . 133 7.4 ThePauliequation ..............................134 7.5 Zeemaneffect .................................137 7.6 Absorptionandemissionoflight. 138 7.7 EinsteinAandBcoefficients. 142 7.8 Quantization of the electromagnetic field . ......144 7.9 Spontaneousemission. 151 7.10 Angulardistributions . 154 7.11 Magnetictransitions . 156 7.12 Photo-electriceffect. 158 7.13 Thomsonscattering. .. .. 160 7.14 Vaccum energies and the cosmological constant . .......163 7.15TheCasimirforce...............................165 8 Spin interactions 169 8.1 Relativistic velocity correction . ......169 8.2 Spin-orbitsplitting . .. .. 171 8.3 Additionofspins ...............................174 8.4 Finestructure.................................177 8.5 Anomalous Zeeman effect and Land´eg-factor . 179 8.6 Hyperfinesplitting ..............................182 8.7 Magnetic transitions in hyperfine doublet . ......186 9 Many-electron atoms 189 6 CONTENTS 9.1 Theheliumatom ...............................189 9.2 Electron spin and the Pauli principle . 193 9.3 Central-fieldapproximation . 196 9.4 TermsandtheHundrules . .. .. .. 200 9.5 Atomicmagneticmoments . 204 9.6 Hartreeapproximations. 205 10 Non-relativistic quantum fields 207 10.1 Identicalparticles . 207 10.2Fockspace...................................210 10.3 Quantumfieldoperators . 213 10.4 Inter-particleinteractions. ......217 10.5Fermions....................................220 10.6Particlesandholes .............................. 222 10.7Latticefieldtheory .............................. 224 Chapter 1 Linear vector spaces The most general formulation of quantum mechanics can be made within the framework of a linear vector space. This is a generalization of ideas we have about ordinary vectors in three-dimensional Euclidean space. We will need vector spaces of higher dimensions. In fact, ordinary quantum-mechanical wavefunctions will be found to be the components of a state vector in a vector space with infinite dimensions. Another generalization will be to consider vectors with components that are not real, but complex numbers. A new scalar product must then be defined. In order to discuss the components, we need to have a basis in the vector space. The values of the components depend on this choice of basis vectors and are related by linear transformations to the components in another basis. When such transformations conserve the lengths of vectors, they are said to be rotations in a real vector space and unitary transformations in a complex vector space. 1.1 Real vector spaces Let us consider a set of vectors x, y, z,... which has the basic property that that sum of any two vectorsV is a new vector{ in the} same set, x + y (1.1) ∈ V Summation is assumed to be commutative, x + y = y + x and associative, (x + y)+ z = x +(y + z). There must also be is null vector 0 such that for any vector x we will have x + 0 = x. The vector which adds to x to give the null vector, is called the inverse vector. These are the basic definitions of a linear vector space. Now to get any further, we must assume that we also have a set of scalars a, b, c, . which we first take to be ordinary, real numbers. Multiplying a vector with such{ a scalar,} we find a new vector, i.e. ax . The linear combination ax + by is therefore also a vector. Multiplying with zero∈ we V get the zero vector. Thus we can write the vector inverse to x to be x. − A vector v is said to be linearly independent of the vectors x, y, z,... when it cannot be written as a linear combination of these vectors. The maxi{ mum number} of linearly independent vectors is called the dimension N of the vector space which now can be 7 8 Chapter 1. Linear vector spaces denoted as N . Such a set is called a basis for the vector space. If this basis set is denoted by e , e ,...,V e , any vector x can therefore be written as the linear combination { 1 2 N } x = x1e1 + x2e2 + . + xN eN or N x = xnen (1.2) nX=1 The scalar coefficients xn are called the components of the vector with respect to this basis. It therefore follows that the components of the sum x + y of two vectors are just the sum xn + yn of their components. Obviously, the components of the null vector are all zero. We have now constructed a linear vector space over real numbers. Measurements in physics are represented by real numbers. For a mathematical construction like a vector space to be physically useful, we must therefore be able to assign sizes or lengths to all vectors in the space. This can be done by endowing the vector space with an inner or scalar product. In analogy with standard vector analysis, we denote the scalar product of a vector x with itself by x x which is then called its squared length and is a positive · number. Similarly, the scalar product of vector x with vector y is written as x y. When this product is zero, we say that the two vectors are normal or orthogonal to each· other. All scalar products are given in terms of the scalar products between the vectors in the basis set. It is most convenient to choose a very special set of such vectors where each is orthogonal to all the others and all have the same length which we take to be one. They are therefore unit vectors. In this orthonormal basis we thus have 1, m = n e e = δ = (1.3) m · n mn 0, m = n 6 where we one the right have introduced the Kroenecker δ-symbol. The scalar product of two vectors x and y is then N N x y = x y e e = x y (1.4) · m n m · n n n m,nX=1 nX=1 and similarly for the squared length of the vector x, N x 2 = x x = x2 (1.5) | | · n nX=1 The length of the null vector is therefore null. Multiplying the vector x with the basis vector en, we find the component of the vector in this direction, x = e x (1.6) n n · Inserting this back into the vector (1.2), we have N x = e e x n n · nX=1 1.2 Rotations 9 Since this is valid for all possible vectors x, we must have that the object N I = enen (1.7) nX=1 acts as a unit operator or identity in the sense that when it acts on any vector, it just gives the same vector back. In fact, we have just shown that I x = x and obviously also I e = e for any basis vector. That the sum in (1.7) is just· the identity, is usually · m m said to show that the basis vectors satisfy the completeness relation. The unit operator I is just one special operator on this vector space. A general operator S acting on a vector x gives a new vector x′, i.e. x′ = S x. We will only consider linear · operators defined by S (x + y) = S x + S y. It is trivial to see from the definition (1.7) that I is linear. Each· operator ·S will have· an inverse denoted by S−1 such that S S−1 = S−1 S = I. · · 1.2 Rotations A rotation of a vector x is a linear transformation of its components so that its length ′ N ′ stays the same. The transformed vector x = n=1 xnen will thus have components P e2 x' x’2 x2 x φ’ α φ x’1 x 1 e1 Figure 1.1: Rotation by an angle α of a two-dimensional vector x into the final vector x′. which in general can be written as N ′ xm = Rmnxn (1.8) nX=1 where the coefficients Rmn are real numbers.