Past exam of the theoretical physics II course of the University of Cambridge 2017 1 c Solution 2026-10-18
At fixed particle number , write and . The contact interaction between two ring modes has energy eigenvaluesFor , the nonnegative product is minimized at the endpoints. ConsequentlyFor this is a two-dimensional degenerate ground state subspace. instead has the unique Fock vacuum. In this projected model, putting all particles into one traveling mode avoids the extra exchange contribution paid when both distinct modes are occupied.
For the alternative coefficients, put and . Then is again minimized at , with . Evenness of is unnecessary for this result; the balanced Fock state maximizes this attractive-interaction energy instead of minimizing it.
Choose the local positive axis along the classical spin. For nonzero field, a proper rotation isIt preserves the Spin commutation relations and turns the field term into . At zero field choose the classical direction , so . Expanding about the original axis without this rotation would put the reference state away from the classical minimum and would not give a controlled small-deviation expansion.
To the required order,The longitudinal exchange gives on each bond. The transverse exchange givesFinally the field contributes its classical constant and . Each site belongs to two bonds, so after removing the order- constant,These are the order- terms; the discarded products of number operators and the next square-root terms are order for occupations held fixed as . A different transverse-axis phase can reverse the sign of without changing the spectrum, but the sign above follows from the stated rotation and oscillator convention.
For the field-free, spin-free linear rigid rotor in one fixed internal quantum state, the electric-dipole interaction is . A nonzero permanent electric dipole moment along the molecular axis allows pure rotational photon absorption with and photon emission with . The matrix element between initial and final quantum states must be nonzero: the existence of an energy gap alone is insufficient. Relative to a chosen axis, polarization of an electromagnetic wave along selects ; transverse polarization of an electromagnetic wave permits .[ref]
Lecture 24 Supplement: Energy levels of a Rigid Rotor by Dudley Herschbach. printed pp. 2–3: dipole transition integrals, polarization and selection rules
Hydrogen chloride and carbon monoxide are examples with a permanent electric dipole moment. By symmetry, molecular hydrogen and carbon dioxide have no permanent electric dipole moment in the ideal symmetric internal state. They still rotate and have rotational energy eigenvalues, but the simple permanent-electric dipole spectrum described here is absent. This restriction concerns this interaction and these assumptions, not every possible way of detecting molecular rotation.
Quantum harmonic oscillator Created 2026-09-24 Updated 2026-10-13
The quantum harmonic oscillator describes a particle of mass in a quadratic potential energy with angular frequency . In the position representation its Quantum Hamiltonian isThe model is useful far beyond a literal spring: a Taylor series about a stable equilibrium with positive potential curvature has this quadratic term as its leading nonconstant approximation. The pure quartic oscillator has zero curvature at its minimum, so that particular approximation does not apply. [ref].
In units with , creation and annihilation operators giveHere is the number operator. Restoring the reduced Planck constant, the energy eigenvalues are for : neighboring levels are separated by , and the ground-state energy is the zero-point energy .
With length scale and dimensionless coordinate , the ground state is the normalized Gaussian wave packetFor , this is precisely the trial wavefunction in the quantum variational principle. The balance of kinetic energy and potential energy therefore recovers the exact ground-state energy using only Gaussian integrals.
Quantum mechanics Created 2026-09-24 Updated 2026-10-18
Quantum mechanics describes a quantum system using a quantum state, with observables represented by self-adjoint operators. For a single particle in one dimension, a pure state can be described by a wavefunction : its squared modulus gives the probability density for position. The Schrödinger equation predicts how this probability amplitude evolves between interventions; measurement in quantum mechanics connects it to experimental outcomes through the Born rule. A wavefunction therefore predicts a distribution of possible positions rather than a single trajectory as in classical mechanics.
The infinite square well makes three central ideas visible with elementary sine functions. Confinement selects discrete energy eigenvalues; wavefunction normalization converts a shape into quantitative probabilities; and a quantum superposition can have a changing probability density even when each constituent energy eigenstate has a stationary one. This combination explains why quantum mechanics uses both linear algebra and differential equations: eigenfunctions describe the building blocks, while quantum phases determine how they interfere. The same tools help explain the discrete energies of chemical atoms and molecules, although their Quantum Hamiltonians require different potentials and often many particles.
In his first 1926 paper, Erwin Schrödinger formulated quantization as an eigenvalue problem for a hydrogen atom in nonrelativistic quantum mechanics. On its opening page he compared the emergence of integers with the number of nodes of a standing wave on a vibrating string. The infinite square well below realizes that appealing idea especially transparently: the allowed integers follow from the boundary conditions. This historical analogy concerns the origin of discrete energies; the Born rule supplies the statistical interpretation of the modern wavefunction. [ref]
Quantisierung als Eigenwertproblem (Erste Mitteilung) by Erwin Schrödinger. Schrödinger, Quantisierung als Eigenwertproblem, 1926, pp. 361–363
. Quantum quench 2026-10-14
A quantum quench changes a quantum system's control parameters rapidly and studies the subsequent unitary time evolution. In the ideal sudden limit, write an initial energy eigenstate using a complete final orthonormal eigenbasis:The Born rule probabilities for a nondegenerate final energy measurement are , with . For a degenerate energy eigenvalue, sum the probabilities over its orthonormal energy eigenstates. Subsequent relative quantum phases can alter other measurement probabilities even though these final energy populations stay fixed. A quench need not begin in an energy eigenstate; the same expansion applies to any initial pure state.
Quantum state continuity at a finite Hamiltonian step Created 2026-10-14 Updated 2026-10-18
For a fixed Hilbert space, a bounded self-adjoint Hamiltonian operator with a finite step at does not deliver an instantaneous rotation of the quantum state. Integrating the Schrödinger equation across a short interval givesFor a normalized quantum state and in operator norm, the difference has norm at most , which tends to zero. The time derivative can jump even though the quantum state is continuous. Here is the reduced Planck constant. An instantaneous replacement of the eigenbasis changes coordinates, not the vector being represented.
For a real switch occupying , remove any real scalar contribution that produces only a global phase, and write . The same integral argument gives the sufficient bounded-model estimateThus controls the sudden approximation up to a global phase. For any normalized final energy eigenstate, its probability amplitude differs from the instantaneous-switch value by at most , and its Born rule probability differs by at most . These are sufficient error bounds, not necessary criteria. For the fixed-gap two-level sudden quench, any switching path with a unit vector has operator norm , giving .
This estimate is deliberately for bounded Hamiltonian operators. An unbounded energy spectrum does not supply a finite global ; relevant quantum states, operator domains and excited energy eigenvalues require separate control. The adiabatic theorem also requires hypotheses about the path and its spectral gaps; there is no universal switch-duration criterion covering all spectra. The cold-atom collapse and revival after a lattice quench illustrates how a single switch can be sudden for one degree of freedom and slow for another.
Quantum variational principle Created 2026-10-03 Updated 2026-10-14
The quantum variational principle estimates the lowest energy by choosing a trial wavefunction and computing its expectation value, without solving the Schrödinger equation exactly. Minimizing over a manageable family of trial wavefunctions gives an upper bound; enlarging that family can improve the estimate.
Let be a self-adjoint operator bounded below, and put . For in its operator domain ,Trial states may also lie in the form domain , where . Then use the quadratic form of a positive quantum Hamiltonian shifted by :This extends the expectation value beyond without requiring to exist. Equality for a normalized state holds exactly in the energy eigenspace at , if that eigenvalue exists. [ref]
https://www.mat.univie.ac.at/~gerald/ftp/book-schroe/schroe.pdf. Gerald Teschl, Mathematical Methods in Quantum Mechanics, Theorem 2.19 and equations (3.50)–(3.51)
.A short proof makes the direction of the bound memorable. If has a complete orthonormal basis of energy eigenstates , writeThe expectation value is a weighted average of allowed energies:Equality requires every occupied energy eigenstate to have energy . [ref]
https://live.ocw.mit.edu/courses/8-05-quantum-physics-ii-fall-2013/61bc31b8d8bf0680c322733910a71aa0_MIT8_05F13_Chap_01.pdf. Barton Zwiebach, MIT 8.05 Wave Mechanics, section 5, Variational Principle
. With continuous spectrum, the spectral theorem replaces the sum by an integral against the scalar spectral measure; the same nonnegative-difference argument works.For an unnormalized trial wavefunction, divide by its squared norm: is the form version of the Rayleigh quotient. The quantum variational principle supplies an upper bound on ; it supplies neither a lower bound on nor, by itself, a guarantee that a bound state exists.
To see the method at work, choose the real Gaussian wave packetThe Gaussian integral gives wavefunction normalization and the two useful position averages:Thus its position probability density is a normal distribution with standard deviation : large means narrow confinement. In units , integration by parts and give the kinetic energyThese smooth, rapidly decaying trial wavefunctions belong to the operator domains of both polynomial Quantum Hamiltonians below. Narrowing the Gaussian wave packet increases its kinetic energy; widening it increases the potential energy in either confining potential.
For the quantum harmonic oscillator, take :The trial values at are respectively . The derivative changes sign at , where kinetic energy and potential energy are both . Here the trial family contains an exact ground state:The zero-point energy remains positive even at the best width. For comparison, removing the potential leaves as : the free Quantum Hamiltonian on the line has spectral bottom zero but no normalizable zero-energy energy eigenstate. A sequence of ever broader trial wavefunctions need not approach an actual bound state.
Gaussian trial widths and the kinetic–potential energy tradeoff
. Normalized Gaussian wave packets with have different position probability densities. The bars show the competing kinetic energy and harmonic potential energy ; their sum is smallest at . Details.For a pure quartic oscillator, keep and set the quartic coefficient to one:The trial values at are respectively . Setting the derivative to zero givesThe sign of this derivative changes from negative to positive at the optimum, giving the smallest energy within this Gaussian wave packet family:At this width, and , so , as expected from the power-law quantum virial theorem for a scale-optimized trial wavefunction. The number is an upper estimate of the ground-state energy, not an asserted exact energy eigenvalue. Indeed,depends on for every , so no member of this trial family is an energy eigenstate. Nevertheless, a single width parameter already turns a difficult Schrödinger equation into a useful, explicit energy estimate.
For , let a unitary operator implement a Lorentz boost taking to . For a Lorentz scalar field, with . The phase follows from translation covariance of a quantum field; its complex conjugate enters the bra. The transformed energy eigenvalue is by invariance of the Minkowski inner product. The reduction requires a massive initial state.
Rotational energy 2026-10-20
For a linear rigid rotor with moment of inertia , the energy eigenvalue at angular momentum quantum number is . Each level has statistical weight before additional symmetry or nuclear-spin restrictions.
Rotational partition functions of hydrogen 2026-10-18
Write the linear rigid rotor energy eigenvalues as , where is the rotational temperature scale, the moment of inertia, the frequency-valued rotational constant, and the Boltzmann constant. Put and . Define sums that include rotational multiplicity but exclude nuclear-spin multiplicity:The canonical partition function for one equilibrating internal rotor is , so its equilibrium orthohydrogen fraction isFor , the lowest allowed levels give and , hence . For , the densely populated even and odd ladders have equal leading sums, , hence . The factor nine belongs to the low-temperature two-level approximation, and the factor three to the high-temperature spin multiplicities.
A frozen mixture requires two separately normalized probability distributions,Multiply these by the prescribed fractions and , respectively. The nuclear-spin factor three cancels from the conditional orthohydrogen distribution. For fixed counts and , the internal part of the many-molecule partition function is proportional to , with combinatorial factors independent of temperature. Its logarithm yields the two conditional means weighted by the fixed counts. Using instead would silently permit conversion and change the physical constraint.
Rotational Raman spectroscopy 2026-10-14
Rotational Raman spectroscopy observes a frequency change of scattered light associated with molecular rotation. The coupling uses the induced electric dipole moment, , where is the electric polarizability tensor. For a linear molecule, the useful anisotropy is : the response differs for an electric field parallel or perpendicular to the molecular axis. A permanent electric dipole moment is not required.[ref]
Absorption lineshapes by Andrei Tokmakoff. Andrei Tokmakoff, §6.2, printed pp. 6-7–6-8, equations (6.40)–(6.44): induced dipole, polarizability tensor and rotational Raman response
For the spin-free linear rigid rotor in one internal quantum state, the anisotropic tensor depends quadratically on the molecular direction. Its angular part has even parity and degree two in spherical harmonics. The triangle inequality for coupled angular momenta permits , and even parity removes odd , leaving . The contribution is unshifted light; shifted rotational lines have . Consequently the rigid-model Stokes shifts, in ordinary frequency units, areSuccessive allowed shifts are separated by , rather than the absorption spacing of pure rotational electric-dipole selection rules. In spectroscopic wavenumber units replace by and by , using the speed of light in for .
A homonuclear diatomic molecule such as molecular hydrogen has no permanent electric dipole moment in its symmetric internal state, so it lacks the ordinary electric-dipole microwave ladder. Its anisotropic electric polarizability can nevertheless give rotational Raman spectroscopy lines. Nuclear-spin symmetry can change the populations of even and odd levels, so the spin-free population example above must not be reused unchanged for molecular hydrogen. The method of coupling, as well as the energy eigenvalues, determines what the experiment can see.
Rotational state populations 2026-10-14
For the spin-free linear rigid rotor in thermal equilibrium at temperature , assume all integer are allowed and ignore nuclear-spin restrictions. Each level has quantum states sharing one energy eigenvalue, an instance of degenerate energy levels, so the Boltzmann distribution givesHere is a rotational partition function, the Planck constant, the Boltzmann constant, and a frequency in . Thus is dimensionless. The factor counts magnetic quantum numbers; it does not mean that a whole level is one quantum state. For the stipulated , the most populated levels are at and at .
Population alone is insufficient to predict intensity. In weak, unsaturated absorption, the integrated absorption coefficient includes the transition frequency, the squared electric dipole moment matrix element, and the difference of lower and upper substate populations because stimulated emission returns energy to the field. A pulsed FTMW spectroscopy signal additionally depends on excitation, quantum coherence, cavity tuning, and receiver response.[ref]
Absorption lineshapes by Andrei Tokmakoff. Andrei Tokmakoff, §§6.1–6.2, printed pp. 6-2–6-6, equations (6.8)–(6.10), (6.27)–(6.29): population difference and rotational dipole matrix elements
For an isotropic sample with polarization of an electromagnetic wave along , write . Normalized spherical harmonics giveThe last equality follows from . Combining this sum with the per-substate Boltzmann distribution and subtracting stimulated emission gives relative integrated absorption areasThe common factor includes and cancels upon normalization. This formula describes integrated weak absorption in a thermal, spin-free linear rigid rotor, not arbitrary peak heights. The example's strongest integrated lines originate at and for and , respectively: they differ from the most populated levels. A missing line can reflect population, coupling, coverage, or sensitivity; it does not prove that the corresponding quantum state is absent.
Spin isomers of hydrogen Created 2026-10-18 Updated 2026-10-20
Spin isomers of hydrogen are two forms of molecular hydrogen, , distinguished by the combined nuclear spin of their two protons. They have the same chemical formula and electronic ground state, but different allowed molecular rotation states. Parahydrogen has total nuclear spin zero and even rotational quantum number ; orthohydrogen has total nuclear spin one and odd . The difference makes heat capacity a probe of fermionic exchange symmetry, and makes cooling history matter for a tank of molecular hydrogen.
Assume the electronic ground state and the vibrational ground state of a free molecule. The electronic factor is symmetric under exchanging the two protons, and the vibrational factor depends only on their separation, so it is also symmetric. These assumptions concern the exchange of protons; the electronic wavefunction separately obeys fermionic exchange symmetry under exchange of electrons. Neglect electronic excitation, vibrational excitation, external fields, and small interactions involving nuclear spin when calculating rotational energy eigenvalues.
The two protons are identical particles with spin . Their complete wavefunction must change sign under their particle exchange operator. Interchanging the two ends reverses the internuclear direction , and the spherical harmonic rotational factor satisfiesThe antisymmetric spin-one-half singlet state therefore requires symmetric, even- rotation; the symmetric spin-one-half triplet state requires antisymmetric, odd- rotation. This is exchange symmetry of two identical spin-one-half fermions applied inside a diatomic molecule, not an extra rotational force. A linear rigid rotor may omit spin-dependent splittings while still requiring this restriction on its allowed quantum states.
Stark effect Created 2026-10-13 Updated 2026-10-18
An electric field shifts and can split the energy eigenvalues of an atom. This is the Stark effect; its hydrogen atom ground-state case is quadratic in a weak field.
The observable in Stark effect spectroscopy is a change in a spectral line, rather than a direct reading of an individual energy eigenvalue. If an upper energy eigenstate emits a photon into a lower energy eigenstate , the Planck constant relates its frequency to the difference:Here denotes the applied electric field component along a chosen axis. Both levels can move, and electric-dipole selection rules for hydrogen decide which pairs produce observable spectral lines. This makes Stark effect spectroscopy a probe of energy eigenstates and their electric dipole moments: the slope is the corresponding dipole component by the Hellmann–Feynman theorem. The comparison with Zeeman splitting is useful: there an applied magnetic field supplies the perturbation.
Stark effect of the hydrogen ground state Created 2026-09-24 Updated 2026-10-20
The even, spherically symmetric hydrogen atom ground state has no permanent electric dipole, so a uniform electric field gives no first-order energy shift. The electric-dipole selection rules for hydrogen allow odd-parity excited states to mix in at second order, yielding a negative shift quadratic in the field.
Here there is a nondegenerate energy eigenvalue, so second-order nondegenerate perturbation theory applies. With , it givesThe notation includes integration over the continuous spectrum, as well as a sum over discrete energy eigenstates. All denominators are negative because is the ground state. The positive electric polarizability therefore lowers its energy.[ref]
Quadratic Stark Effect. Quantum Mechanics by Richard Fitzpatrick; Fitzpatrick, Quadratic Stark Effect, equations (7.57) and (7.65): quadratic convention and exact polarizability
An independent way to see the coefficient avoids truncating that sum. Define and . In coordinates , the dimensionless unperturbed Hamiltonian operator and normalized wavefunction are and , with energy eigenvalue . Writing the first-order wavefunction correction as , substitution into the time-independent Schrödinger equation givesThe second equality can be checked by differentiation. Its parity makes orthogonal to . The resulting integral issince the normalized radial probability density is , giving and . Converting back to SI units gives the stated electric polarizability. The induced electric dipole moment is and tends to zero with the electric field, unlike the selected degenerate branches' leading dipoles. Both calculations describe weak-field level shifts; a spatially uniform static electric field also allows eventual quantum tunnelling and ionization, which these real energy corrections do not calculate.
Stern-Gerlach force and flight model 2026-10-18
Let the atomic beam travel along , with velocity , and let measure displacement along the dominant magnetic field gradient. For a fixed effective magnetic moment component , the magnetic dipole potential energy is . Taking its negative partial derivative givesA spatially uniform magnetic field can produce torque and Larmor precession, but cannot produce this translational separation. In a quantum state following a local internal energy eigenvalue , the more general expression is , with effective magnetic moment . Treating that moment as constant is an approximation with a physical regime, not an extra measured fact. Assume the local magnetic field direction stays nearly fixed across the sampled beam, and that internal states follow it without transitions, as in the adiabatic theorem. The scalar gradient model describes the beam's neighborhood; it omits the full magnetic field's transverse components and fringe regions.
Assume a constant over magnet length , followed by a field-free drift . Neglect transverse motion at entry and changes in longitudinal velocity. Newton's second law gives transverse acceleration for whole-atom mass . The magnet transit time is , and the drift time is . The magnet supplies both a displacement and an exit transverse velocity:The contribution is motion with the acquired transverse velocity, not continued acceleration outside the magnet. For the plate-at-exit geometry, set . For a nonzero entrance transverse velocity , add . These terms show why initial collimation and flight geometry matter when inferring a magnetic moment from a deposit.
Choose hypothetical parameters , , , , and . Approximate the two effective magnetic moments by , where the Bohr magneton is . Then , and . The positive displacement is about inside the magnet plus during drift: , with full separation . These chosen values illustrate the model and are not reconstructed 1922 measurements.
The exit transverse velocity is only about , small compared with the chosen forward velocity; this checks the small-deflection assumption. Halving halves , doubling divides by four, and setting removes most of this example's separation. A real pole has fringe magnetic fields and a position-dependent gradient; these require a more complete trajectory calculation.
Stipulated bond dissociation model 2026-10-13
Take an invented diatomic molecule with a Morse potential, setting the separated-atom energy to zero:Here is an inverse length, the equilibrium bond length, and , with reduced mass . These stipulated parameters describe a simple model, not a measured chemical substance. For the one-dimensional Morse oscillator, energy eigenvalues above the minimum areConsequently,The harmonic estimate is slightly larger than this model's exact zero-point energy. The physical bound-level restriction matters: the quadratic expression is not an infinite ladder of vibrational quantum states.
Bond potential-well depth and ground-state dissociation energy reach the same separated-atom limit from different starting energies
. Original stipulated Morse potential with and . The horizontal coordinate is ; the horizontal line is an energy eigenvalue, not a classical trajectory or a measured spectrum. Details.For a separate thermal illustration using this same stipulated , assume an ideal gas, fully active molecular rotation of the parent, negligible thermal molecular vibration, and negligible electronic excitation for all species. Each monatomic product contributes ; the diatomic molecule contributes . Thus the net increment is , with molar gas constant . At ,This last result follows from the stated thermal model, not a universal correction for every chemical bond. Frozen rotations, accessible excited states, different fragment composition, or a condensed phase change the thermal increments.
Consider an original ideal quantum system with positive scales andInterpret as one component of an electric dipole moment, so its coupling to the corresponding electric field is the electric-dipole interaction . The gaps are , but : this interaction has no direct first-order coupling. The nonzero squared matrix elements are and . These are coupling weights; actual spectral line intensities also depend on populations and radiation factors. In particular, there is no promise that an experiment populates the upper state of every allowed transition.
A measurement of itself has possible outcomes , sinceThese are eigenvalues of , not the energy eigenvalues . Moreover, although : two factors connect through . This algebraic statement does not turn into a nonzero direct coupling. Higher-order probability amplitudes for transitions require the appropriate dynamical calculation.




