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CRC Press eBooks

Quantum transition

Tao Xiang

Published Mar 31, 2022• 0 citations
Publisher

Abstract

A small parameter is used to identify the orders of perturbation. The unperturbed Hamiltonian is assumed time-independent and can be diagonalized. The interaction of an electron with an applied electromagnetic field is governed by the gauge-invariant Hamiltonian. If both the initial and final energy levels are discretized, the delta function indicates that the transition happens only when the energy difference between the two levels matches the frequency of the perturbation. The delta function suggests that the absorption or stimulated emission happens only when the energy difference between the final and initial states matches precisely the frequency of the applied electromagnetic wave. The quantum transition induced by a monochromatic perturbation is determined by the matrix element between the initial and final states.

DOI
10.1201/9781003174882-10

Related papers

Complement 1B: Transition induced by a random broadband perturbation

G. Grynberg, Alain Aspect, Claude Fabre +1 more

We have seen in Section 1.2 that a transition between two discrete levels | i 〉 and | k 〉 is possible when the system is submitted to a perturbation which has a non-zero Fourier component close to the Bohr frequency ω 0 = ( E k − E i )/ħ of the transition. This is the case when the perturbation Ĥ 1 ( t ) is sinusoidal, of the form Ĥ 1 ( t ) = Ŵ cos(ω t + φ), and oscillates at a frequency ω close to ω 0 . But in many real physical situations, the perturbation is not perfectly mastered: it is a pure sine function only for times shorter than a limit, called the coherence time . At longer times, the oscillating perturbation has a phase and an amplitude that vary randomly. This is, for example, the case when the perturbation is due to an incident electromagnetic wave produced by a thermal lamp, in which the thermal fluctuations induce random variations of the amplitude and phase of the wave. As the perturbation is no longer a pure sinusoidal wave, its Fourier spectrum is no longer a Dirac delta function. It has some finite width around a mean frequency. For this reason a random perturbation is also called a ‘broadband’ perturbation. We shall determine in this complement the temporal evolution of the quantum system submitted to such a random perturbation. We shall see that the transition probability between two discrete levels is proportional to T for small interaction time T , and has an exponential behaviour at long times, a result which is very similar to that obtained for a transition between a discrete level and a continuum.

Cambridge University Press eBooks•Sep 2, 2010•0 citations

Tutorial: Perturbation Approximations to Asymptotic Quantum Transition Rates

Steven Kenneth Kauffmann

The orders of the perturbation approximation to the Schroedinger-picture time evolution operator in powers of the presumed-small perturbation part of the Hamiltonian operator are developed by the iteration of an identity; the possibly confusing switch to the interaction picture isn't needed. Those time-evolution operator approximations are sandwiched between two orthogonal, normalized eigenstates of the unperturbed part of the Hamiltonian operator to produce the transition amplitude approximations, whose calculation is reduced to quadrature when every occurrence of the perturbation part of the Hamiltonian operator in them is expanded in the unperturbed basis. That expansion also reveals the time-dependent parts of those approximations to be multiply nested integrals which in the long-time limit approach simple products of non-singular inverses (principle value plus delta function) of differences of unperturbed energy eigenvalues. Closely related to the long-time limits of transition amplitudes are the long-time averages of transition rates. When the unperturbed basis is that of free-particle states, sums over relevant final states of transition rates from an initial state, divided by the initial state's particle flux, produce cross sections. Here the perturbation approximations to generic quantum transition rates are parlayed to the corresponding approximations to differential cross sections for nonrelativistic-particle potential scattering.

•Aug 1, 2019•0 citations

TIME-DEPENDENT PERTURBATION METHODS

Vishnu S. Mathur, Surendra Singh

We now consider systems for which the Hamiltonian contains time-dependent interaction terms. In such cases we cannot reduce the time-dependent Schro¨dinger equation to an eigenvalue equation. However, if the time-dependent terms can be regarded as small perturbations, we can develop a form of perturbation theory that can be used to calculate the effects of time-dependent terms. Consider a system for which the Hamiltonian may be written as the sum of a dominant unperturbed part Hˆ0 and a small perturbation Hˆ ′ as Hˆ = Hˆ0 + λHˆ ′(t) , (10.1.1) where the unperturbed Hamiltonian Hˆ0 is independent of time, whereas the perturbation Hˆ ′ may depend on time. The parameter 0 < λ < 1 has been introduced to keep track of various orders of approximations as in the case of time-independent perturbation theory discussed in Chapter 8. The basic idea is that a small perturbation to the Hamiltonian will produce a small change in the wave function. For a time-dependent perturbation, this change means that a system, initially in a particular eigenstate of Hˆ0, will find itself in a time-dependent admixture of the eigenstates. Thus the time-dependent perturbation causes the system to undergo transition to different eigenstates of Hˆ0. So for time-dependent perturbations our interest lies in calculating the probabilities for transition to different states.

Chapman & Hall/CRC eBooks•Dec 12, 2008•0 citations

Light-Matter Interactions

Ying Fu, Min Qiu

We start the discussion by a formal theory of perturbation, which will be further elucidated by straightforward calculations. 2.1.1 The Golden Rule Assume that H0 is a time-independent Hamiltonian and all solutions of the eigenvalue problem H0|k〉 = Ek|k〉 are known; it is straightforward to construct the solution of the equation of motion i ∂|ψ(t)〉 ∂t = H0|ψ(t)〉 (2.1) which coincides at t = 0 with the given initial state |ψ(0)〉. Under these circumstances, the state vector |ψ(t)〉 = e−iH0t/|ψ(0) (2.2) represents the general solution of the equation of motion, Eq. 2.1. Since∑ |k〉〈k| = 1 we obtain |ψ(t)〉 = ∑ k e−iH0t/|k〉〈k|ψ(0)〉 = ∑ k e−iEkt/|k〉〈k|ψ(0)〉 (2.3) We now calculate transition amplitudes between the relevant unperturbed eigenstates due to the appearance of an external perturbation V at t = 0. We transform the equation of motion in the Schro¨dinger picture i ∂|ψ(t)〉 ∂t = (H0 + V )|ψ(t)〉 (2.4) to the interaction picture by a time-dependent unitary operator |ψˆ(t)〉 = exp (iH0t/)|ψ(t)〉 (2.5) so that in the interaction picture, the equation of motion for the state is i ∂|ψˆ(t)〉 ∂t = Vˆ (t)|ψˆ(t)〉 (2.6) where the new interaction operator is given by Vˆ (t) = exp (iH0t/)V exp (−iH0t/) (2.7) Next we introduce a time development operator Tˆ (t) such that |ψˆ(t)〉 = Tˆ (t)|ψˆ(0)〉 (2.8) The time development operator satisfies the integral equation Tˆ (t) = 1− i Vˆ (t)Tˆ (t′)dt′ (2.9) The relationship between the operator expressions in the two pictures is Tˆ (t) = exp (iH0t/)T (t) exp (−iH0t/) (2.10) The transition matrix elements of the time development operator between eigen- states of the unperturbed Hamiltonian are 〈q|Tˆ (t)|k〉 = δ(q − k)− i 〈q|Vˆ (t)Tˆ (t′)|k〉dt′ = δ(q − k)− i 〈q|Vˆ (t′)|k′〉〈k′|Tˆ (t′)|k〉dt′ (2.11) By Eq. 2.10, and note H0|k〉 = Ek|k〉 and H0|q〉 = Eq|q〉, 〈q|Tˆ (t)|k〉 = δ(q − k)− i ei(Eq−Ek′ )t ′/〈q|V (t′)|k′〉〈k′|Tˆ (t′)|k〉dt′ (2.12) The strategy of time-dependent perturbation theory is to assume that V is small and proceed with iterating Eq. 2.9 as a power series in terms of Vˆ Tˆ (t) = 1− i Vˆ ′dt′ − 1 2 Vˆ ′′dt′′ + · · · (2.13) and the transition amplitude from initial state |k〉 to final state |q〉 in the perturbation expansion becomes 〈q|Tˆ (t)|k〉 = δ(q − k)− i − 1 2 × ∫ t′ 0 ei(Ek′−Ek)t ′′/〈k′|V (t′′)|k〉dt′dt′′ + · · · (2.14) It is equivalent to obtain the above equation by iteratively replacing the term 〈k′|Tˆ (t′)|k〉 on the right side of Eq. 2.12 by the whole right-side expression of Eq. 2.12, i.e., ∑ k′ = ∫ t′ 0 + ∑ k′ =k ei(Eq−Ek′ )t ′′/〈q|V (t′′)|k′〉〈k′|Tˆ (t′′)|k〉dt′′ (2.15) By Eq. 2.12 〈k|Tˆ (t′)|k〉 = 1− i ei(Ek−Ek′′ )t ′′/〈k|V (t′′)|k′′〉〈k′′|Tˆ (t′′)|k〉dt′′ (2.16) The first term on the right side of the above equation results in the second term on the right side of Eq. 2.14. For k′ = k and by Eq. 2.12, the second term on the right side of Eq. 2.15 becomes 〈k′|Tˆ (t′)|k〉 = − i ei(Ek′−Ek′′ )t ′′/〈k′|V (t′′)|k′′〉〈k′′|Tˆ (t′′)|k〉dt′′ (2.17) We use Eq. 2.15 to separate the term k′′ = k from k′′ = k in the above equation, which becomes the third term on the right side of Eq. 2.14.

•Aug 8, 2011•0 citations

Transitions

P. C. W. Davies, David S. Betts

In many practical cases a stationary system is perturbed in some way, inducing it to undergo transitions between the otherwise stationary states. Perhaps the best example concerns the radiative transitions of atomic electrons in which the disturbance of an external electromagnetic field causes the electrons to jump between energy levels, emitting or absorbing photons. Equation is a statement of the classical law of conservation of energy. The stimulated emission and absorption of radiation both have close classical analogues. If a simple harmonic oscillator is driven by a sinusoidal electromagnetic field it can gain or lose energy depending on phase angles. The existence of spontaneous emission implies that all excited states of electrical systems are unstable and will eventually decay to the ground state by photon emission. Quantum systems thus comply with the fundamental principle that physical systems tend to seek out their state of lowest energy and maximum entropy.

Routledge eBooks•Apr 27, 2018•0 citations

ATOMIC RADIATION

Mircea S. Rogalski, Stuart B. Palmer

During the presence of the radiation perturbation ( ),ˆ tV the Hamiltonian of the system becomes ( )tVHH ˆˆˆ 0 += (37.4) and, since the state of the system varies with time, we must adopt the time-dependent Schrödinger equation to be a basis for the perturbation theory, that is ( ) ( ) ( )0ˆ ˆti H V tt ∂Ψ ⎡ ⎤= + Ψ⎣ ⎦∂= t (37.5) We assume that Eq.(37.5) has normalized solutions which can be expanded in terms of the as 0kΨ t a t t a t e ε−Ψ = Ψ = Ψ∑ ∑ = (37.6) where the normalization condition on ( )tΨ gives a t =∑ (37.7) that is, ( ) 2ka t gives the probability that the system is in the state at time t. Substituting Eq.(37.6) into Eq.(37.5) yields da t ii a t e V t a t e dt ε εε ε− −⎡ ⎤ ⎡ ⎤− Ψ = +⎢ ⎥ ⎣ ⎦⎣ ⎦∑ ∑ = == = which reduces to da t i e V t a t e dt ε− k ε−Ψ = Ψ∑ ∑= == (37.8) In view of orthogonality of the stationary state eigenfunctions, multiplication by ( ) followed by integration over the configuration space gives da t i e a t e V t dt ε εδ− −= Ψ Ψ∑ ∑= == (37.9) Denoting the matrix elements of the perturbation operator between the stationary states n and k by ( ) ( )0 ˆnk n kV t V t 0= Ψ Ψ (37.10) we can rewrite Eq.(37.9) as da t i a t V t e dt ε ε−= ∑ == (37.11) which is a set of simultaneous differential equations of the first order for the coefficients ( ).na t If we assume that the system is in a definite stationary state at some 0iΨ particular time 0,t = and then it is allowed to interact with the radiation field, we obtain from Eq.(37.6) that ( ) ( )0 00 0i k k aΨ = Ψ = Ψk∑ Multiplying by and integrating gives ( )∗Ψ 0k ( )0ka kiδ= (37.12) that is, and for .( ) 10 =ia ( ) 00 =ka ik ≠ If we consider a time interval t sufficiently short for the coefficients in Eqs.(37.11) to be approximated by the form (37.12), which means that the term gives the greatest contribution to the sum and all other terms can be neglected, we have ( )tak ik = ( ) ( ) ( )0 0 /n ii tn nida ti V t edt ε ε−= == , ( ) ( ) ( )i i iida ti a t Vdt == t (37.13) and on integration we obtain ( ) ( ) ( ) (0 0 / 0 ia t V t e dt n iε ε ′− ′= − ≠∫ == ) , ( ) ( ) tdtVita iii ′′−= ∫ 0 1 = (37.14) The probability (29.29) that the system is in the state at time t, in other words, that coincides with is given by ( )tΨ ,0nΨ ( ) ( ) ( )2 20in n nP t t a t= Ψ Ψ = (37.15) and this is taken to be the probability of direct transition from state to state in a time t, induced by the presence of the radiation field. Assuming a transition where a photon is emitted, that is, we recall the Bohr condition (28.19), which reads ,00 ni εε > (37.16) inni ωεε ==− 00 so that Eqs.(37.14) can be rewritten as ( ) ( ) ( ) 0 n ni ia t V t e dt n iω ′−′ ′= − ≠∫= (37.17) ( ) ( ) 0 1 t i ii ia t V t dt′ ′= − ∫= As we can see from the above, the time-dependent perturbation theory is concerned with transitions that result from perturbation, between the unperturbed levels of the system, while time-independent perturbation theory calculates the stationary shifts in the energy levels. 37.2. FERMI'S GOLDEN RULE Consider the case of a constant perturbation, switched on at time The integrals (37.17) become straightforward, and we obtain .0=t ( ) ( ) ( )1ini tnin in Va t e n iωω −= − ≠= (37.18) ( ) tVita iii =−=1 Substituting Eqs.(37.18) into Eq.(37.6) gives, to a first approximation, the wave function of the atomic system as Vt e t e tωω − − ≠ Ψ = Ψ + − Ψ∑= = (37.19) The probability (37.15) of observing the system in the state at time t, for the coefficients given by Eq.(37.18), reduces to 0 nΨ( )tan ( ) ( 2/sin4 222 2 t V ni in ωω== ) (37.20) which means that transitions from state to states only take place if the matrix elements do not vanish. The plot of niV ( )tPin as a function of inω , given in Figure 37.1 for a perturbation which is on for a time t, suggests that the probability behaves like a Dirac δ -function as t approaches infinity. We may represent the δ -function as ( ) dxe t t 2 1lim 2/ 2/sin lim ωππω ω ( ) ( ininxi dxe in ωδωδπ ω 22/2 1 2/ === ∫ ∞ ∞− ) (37.21) where use was made of a property derived from the normalization condition, written as ( ) ( ) ( ) ( ) ( )u k kukudkuduu δδδδ 1or1 === ∫∫ ∞ P t( ) ω4π6π t2π in t-t-t 2π 4π t 6π t0 Figure 37.1. Dependence of the transition probability on frequency It follows from Figure 37.1 that, in the large-t limit, we have ,0≅inω and hence ( )2sin / 2 / 1.in int tω ω⎡ →⎣ ⎤⎦ Thus, one obtains ( ) ( ) ( ) ( ) (2 24sin / 2 sin / 2 sin / 2lim lim / 2 2/ 2 / 2in in in in int t in inin t t t tt ω ω ω )π πδ ω πδ ωω πωω→∞ →∞ ⎡ ⎤= =⎢ ⎥⎣ ⎦ = so that the transition probability becomes ( ) ( ) (2 2 0 022 2lim in ni in ni i nt t tP t V Vπ π )δ ω δ ε→∞ = = == ε− (37.23) It follows that the transitions take place between states of equal unperturbed energies The transition probability is proportional to the time interval t during which the perturbation is on, that is .00 in εε → ( )tPin approaches infinity as .∞→t Since no experiment lasts for an infinite time, it is the transition probability per unit time, called the transition rate , which is of particular interest. Normally, is part of a continuum, and hence, the transition might end in any state which belongs to a finite range of N final states, rather than in a particular state. We may then define the transition rate as ( )dNtP t P intni ∫∞→→ = 1lim (37.24) The integral over the final states is usually transformed into one over energy, if we define a density of states ( ) ,ρ ε representing the number of continuum states per energy interval, by taking ( )0ndN d 0nρ ε ε= (37.25) so that, substituting Eqs.(37.23) and (37.25), Eq.(37.24) gives ( ) ( ) ( ) ( )20 0 0 0 01 2limi n in n n ni n i ntP P t d Vt πρ ε ε ρ ε δ ε ε→ →∞= =∫ = − (37.26) This result is known as Fermi's golden rule, which states that transitions may occur only between states of equal energies for which the matrix elements of the perturbation operator do not vanish, and that the transition rate is proportional to both the square modulus of these matrix elements and the density of final states. 37.3. EMISSION AND ABSORPTION OF RADIATION Consider the transitions between stationary states which are induced by a harmonic perturbation of the form ( ) ( ) ( ) ( ) ( )( )titi eeArVtArVtV ωωωωω −+== GG ˆcosˆ2ˆ (37.27) It is assumed that the harmonic perturbation corresponds to the interaction of either the electric or magnetic field components of the incoming radiation with the electric or magnetic moment of the atom. Thus, the coupling between the system and the perturbing field can be taken in the form of a field amplitude ( )ωA times a displacement of the system ( ).ˆ rV G On substitution of Eq.(37.27) into Eq.(37.10) one obtains ( ) ( ) ( )( ) ( )( )titinititiinni eeAVeeArVtV ωωωω ωω −− +=+ΨΨ= 00 ˆ G (37.28) It follows from Eq.(37.17) that n ni ia t V A e e dtω ω ω ωω ′ ′− − − +⎡ ⎤ ′= − +⎣ ⎦∫= (37.29) inin eeAV 0 ⎥⎦ ⎤⎢⎣ ⎡ ++−= ωωωω ω ωωωω V A e eω ω ω ωω ω ω ω ω − − − +⎡ ⎤− −= +⎢ ⎥− +⎢ ⎥⎣ ⎦= If the atomic system is bathed into a radiation field of frequency ,inni ωωω −== which implies that according to the Bohr condition (37.16), the transition from state to state describes a process of induced absorption, where the energy of the system is increased by energy transfer from the radiation field to the atom. If 00 in εε > ,ni inω ω ω= = − the second term on the right-hand side of Eq.(37.29) grows without limit, so that the first term can be neglected.

CRC Press eBooks•Jan 8, 2014•0 citations
A small parameter is used to identify the orders of perturbation. The unperturbed Hamiltonian is assumed time-independent and can be diagonalized. The interaction of an electron with an applied electromagnetic field is governed by the gauge-invariant Hamiltonian. If both the initial and final energy levels are discretized, the delta function indicates that the transition happens only when the energy difference between the two levels matches the frequency of the perturbation. The delta function suggests that the absorption or stimulated emission happens only when the energy difference between the final and initial states matches precisely the frequency of the applied electromagnetic wave. The quantum transition induced by a monochromatic perturbation is determined by the matrix element between the initial and final states.
We have seen in Section 1.2 that a transition between two discrete levels | i 〉 and | k 〉 is possible when the system is submitted to a perturbation which has a non-zero Fourier component close to the Bohr frequency ω 0 = ( E k − E i )/ħ of the transition. This is the case when the perturbation Ĥ 1 ( t ) is sinusoidal, of the form Ĥ 1 ( t ) = Ŵ cos(ω t + φ), and oscillates at a frequency ω close to ω 0 . But in many real physical situations, the perturbation is not perfectly mastered: it is a pure sine function only for times shorter than a limit, called the coherence time . At longer times, the oscillating perturbation has a phase and an amplitude that vary randomly. This is, for example, the case when the perturbation is due to an incident electromagnetic wave produced by a thermal lamp, in which the thermal fluctuations induce random variations of the amplitude and phase of the wave. As the perturbation is no longer a pure sinusoidal wave, its Fourier spectrum is no longer a Dirac delta function. It has some finite width around a mean frequency. For this reason a random perturbation is also called a ‘broadband’ perturbation. We shall determine in this complement the temporal evolution of the quantum system submitted to such a random perturbation. We shall see that the transition probability between two discrete levels is proportional to T for small interaction time T , and has an exponential behaviour at long times, a result which is very similar to that obtained for a transition between a discrete level and a continuum.
The orders of the perturbation approximation to the Schroedinger-picture time evolution operator in powers of the presumed-small perturbation part of the Hamiltonian operator are developed by the iteration of an identity; the possibly confusing switch to the interaction picture isn't needed. Those time-evolution operator approximations are sandwiched between two orthogonal, normalized eigenstates of the unperturbed part of the Hamiltonian operator to produce the transition amplitude approximations, whose calculation is reduced to quadrature when every occurrence of the perturbation part of the Hamiltonian operator in them is expanded in the unperturbed basis. That expansion also reveals the time-dependent parts of those approximations to be multiply nested integrals which in the long-time limit approach simple products of non-singular inverses (principle value plus delta function) of differences of unperturbed energy eigenvalues. Closely related to the long-time limits of transition amplitudes are the long-time averages of transition rates. When the unperturbed basis is that of free-particle states, sums over relevant final states of transition rates from an initial state, divided by the initial state's particle flux, produce cross sections. Here the perturbation approximations to generic quantum transition rates are parlayed to the corresponding approximations to differential cross sections for nonrelativistic-particle potential scattering.
We now consider systems for which the Hamiltonian contains time-dependent interaction terms. In such cases we cannot reduce the time-dependent Schro¨dinger equation to an eigenvalue equation. However, if the time-dependent terms can be regarded as small perturbations, we can develop a form of perturbation theory that can be used to calculate the effects of time-dependent terms. Consider a system for which the Hamiltonian may be written as the sum of a dominant unperturbed part Hˆ0 and a small perturbation Hˆ ′ as Hˆ = Hˆ0 + λHˆ ′(t) , (10.1.1) where the unperturbed Hamiltonian Hˆ0 is independent of time, whereas the perturbation Hˆ ′ may depend on time. The parameter 0 < λ < 1 has been introduced to keep track of various orders of approximations as in the case of time-independent perturbation theory discussed in Chapter 8. The basic idea is that a small perturbation to the Hamiltonian will produce a small change in the wave function. For a time-dependent perturbation, this change means that a system, initially in a particular eigenstate of Hˆ0, will find itself in a time-dependent admixture of the eigenstates. Thus the time-dependent perturbation causes the system to undergo transition to different eigenstates of Hˆ0. So for time-dependent perturbations our interest lies in calculating the probabilities for transition to different states.
We start the discussion by a formal theory of perturbation, which will be further elucidated by straightforward calculations. 2.1.1 The Golden Rule Assume that H0 is a time-independent Hamiltonian and all solutions of the eigenvalue problem H0|k〉 = Ek|k〉 are known; it is straightforward to construct the solution of the equation of motion i ∂|ψ(t)〉 ∂t = H0|ψ(t)〉 (2.1) which coincides at t = 0 with the given initial state |ψ(0)〉. Under these circumstances, the state vector |ψ(t)〉 = e−iH0t/|ψ(0) (2.2) represents the general solution of the equation of motion, Eq. 2.1. Since∑ |k〉〈k| = 1 we obtain |ψ(t)〉 = ∑ k e−iH0t/|k〉〈k|ψ(0)〉 = ∑ k e−iEkt/|k〉〈k|ψ(0)〉 (2.3) We now calculate transition amplitudes between the relevant unperturbed eigenstates due to the appearance of an external perturbation V at t = 0. We transform the equation of motion in the Schro¨dinger picture i ∂|ψ(t)〉 ∂t = (H0 + V )|ψ(t)〉 (2.4) to the interaction picture by a time-dependent unitary operator |ψˆ(t)〉 = exp (iH0t/)|ψ(t)〉 (2.5) so that in the interaction picture, the equation of motion for the state is i ∂|ψˆ(t)〉 ∂t = Vˆ (t)|ψˆ(t)〉 (2.6) where the new interaction operator is given by Vˆ (t) = exp (iH0t/)V exp (−iH0t/) (2.7) Next we introduce a time development operator Tˆ (t) such that |ψˆ(t)〉 = Tˆ (t)|ψˆ(0)〉 (2.8) The time development operator satisfies the integral equation Tˆ (t) = 1− i Vˆ (t)Tˆ (t′)dt′ (2.9) The relationship between the operator expressions in the two pictures is Tˆ (t) = exp (iH0t/)T (t) exp (−iH0t/) (2.10) The transition matrix elements of the time development operator between eigen- states of the unperturbed Hamiltonian are 〈q|Tˆ (t)|k〉 = δ(q − k)− i 〈q|Vˆ (t)Tˆ (t′)|k〉dt′ = δ(q − k)− i 〈q|Vˆ (t′)|k′〉〈k′|Tˆ (t′)|k〉dt′ (2.11) By Eq. 2.10, and note H0|k〉 = Ek|k〉 and H0|q〉 = Eq|q〉, 〈q|Tˆ (t)|k〉 = δ(q − k)− i ei(Eq−Ek′ )t ′/〈q|V (t′)|k′〉〈k′|Tˆ (t′)|k〉dt′ (2.12) The strategy of time-dependent perturbation theory is to assume that V is small and proceed with iterating Eq. 2.9 as a power series in terms of Vˆ Tˆ (t) = 1− i Vˆ ′dt′ − 1 2 Vˆ ′′dt′′ + · · · (2.13) and the transition amplitude from initial state |k〉 to final state |q〉 in the perturbation expansion becomes 〈q|Tˆ (t)|k〉 = δ(q − k)− i − 1 2 × ∫ t′ 0 ei(Ek′−Ek)t ′′/〈k′|V (t′′)|k〉dt′dt′′ + · · · (2.14) It is equivalent to obtain the above equation by iteratively replacing the term 〈k′|Tˆ (t′)|k〉 on the right side of Eq. 2.12 by the whole right-side expression of Eq. 2.12, i.e., ∑ k′ = ∫ t′ 0 + ∑ k′ =k ei(Eq−Ek′ )t ′′/〈q|V (t′′)|k′〉〈k′|Tˆ (t′′)|k〉dt′′ (2.15) By Eq. 2.12 〈k|Tˆ (t′)|k〉 = 1− i ei(Ek−Ek′′ )t ′′/〈k|V (t′′)|k′′〉〈k′′|Tˆ (t′′)|k〉dt′′ (2.16) The first term on the right side of the above equation results in the second term on the right side of Eq. 2.14. For k′ = k and by Eq. 2.12, the second term on the right side of Eq. 2.15 becomes 〈k′|Tˆ (t′)|k〉 = − i ei(Ek′−Ek′′ )t ′′/〈k′|V (t′′)|k′′〉〈k′′|Tˆ (t′′)|k〉dt′′ (2.17) We use Eq. 2.15 to separate the term k′′ = k from k′′ = k in the above equation, which becomes the third term on the right side of Eq. 2.14.
In many practical cases a stationary system is perturbed in some way, inducing it to undergo transitions between the otherwise stationary states. Perhaps the best example concerns the radiative transitions of atomic electrons in which the disturbance of an external electromagnetic field causes the electrons to jump between energy levels, emitting or absorbing photons. Equation is a statement of the classical law of conservation of energy. The stimulated emission and absorption of radiation both have close classical analogues. If a simple harmonic oscillator is driven by a sinusoidal electromagnetic field it can gain or lose energy depending on phase angles. The existence of spontaneous emission implies that all excited states of electrical systems are unstable and will eventually decay to the ground state by photon emission. Quantum systems thus comply with the fundamental principle that physical systems tend to seek out their state of lowest energy and maximum entropy.
During the presence of the radiation perturbation ( ),ˆ tV the Hamiltonian of the system becomes ( )tVHH ˆˆˆ 0 += (37.4) and, since the state of the system varies with time, we must adopt the time-dependent Schrödinger equation to be a basis for the perturbation theory, that is ( ) ( ) ( )0ˆ ˆti H V tt ∂Ψ ⎡ ⎤= + Ψ⎣ ⎦∂= t (37.5) We assume that Eq.(37.5) has normalized solutions which can be expanded in terms of the as 0kΨ t a t t a t e ε−Ψ = Ψ = Ψ∑ ∑ = (37.6) where the normalization condition on ( )tΨ gives a t =∑ (37.7) that is, ( ) 2ka t gives the probability that the system is in the state at time t. Substituting Eq.(37.6) into Eq.(37.5) yields da t ii a t e V t a t e dt ε εε ε− −⎡ ⎤ ⎡ ⎤− Ψ = +⎢ ⎥ ⎣ ⎦⎣ ⎦∑ ∑ = == = which reduces to da t i e V t a t e dt ε− k ε−Ψ = Ψ∑ ∑= == (37.8) In view of orthogonality of the stationary state eigenfunctions, multiplication by ( ) followed by integration over the configuration space gives da t i e a t e V t dt ε εδ− −= Ψ Ψ∑ ∑= == (37.9) Denoting the matrix elements of the perturbation operator between the stationary states n and k by ( ) ( )0 ˆnk n kV t V t 0= Ψ Ψ (37.10) we can rewrite Eq.(37.9) as da t i a t V t e dt ε ε−= ∑ == (37.11) which is a set of simultaneous differential equations of the first order for the coefficients ( ).na t If we assume that the system is in a definite stationary state at some 0iΨ particular time 0,t = and then it is allowed to interact with the radiation field, we obtain from Eq.(37.6) that ( ) ( )0 00 0i k k aΨ = Ψ = Ψk∑ Multiplying by and integrating gives ( )∗Ψ 0k ( )0ka kiδ= (37.12) that is, and for .( ) 10 =ia ( ) 00 =ka ik ≠ If we consider a time interval t sufficiently short for the coefficients in Eqs.(37.11) to be approximated by the form (37.12), which means that the term gives the greatest contribution to the sum and all other terms can be neglected, we have ( )tak ik = ( ) ( ) ( )0 0 /n ii tn nida ti V t edt ε ε−= == , ( ) ( ) ( )i i iida ti a t Vdt == t (37.13) and on integration we obtain ( ) ( ) ( ) (0 0 / 0 ia t V t e dt n iε ε ′− ′= − ≠∫ == ) , ( ) ( ) tdtVita iii ′′−= ∫ 0 1 = (37.14) The probability (29.29) that the system is in the state at time t, in other words, that coincides with is given by ( )tΨ ,0nΨ ( ) ( ) ( )2 20in n nP t t a t= Ψ Ψ = (37.15) and this is taken to be the probability of direct transition from state to state in a time t, induced by the presence of the radiation field. Assuming a transition where a photon is emitted, that is, we recall the Bohr condition (28.19), which reads ,00 ni εε > (37.16) inni ωεε ==− 00 so that Eqs.(37.14) can be rewritten as ( ) ( ) ( ) 0 n ni ia t V t e dt n iω ′−′ ′= − ≠∫= (37.17) ( ) ( ) 0 1 t i ii ia t V t dt′ ′= − ∫= As we can see from the above, the time-dependent perturbation theory is concerned with transitions that result from perturbation, between the unperturbed levels of the system, while time-independent perturbation theory calculates the stationary shifts in the energy levels. 37.2. FERMI'S GOLDEN RULE Consider the case of a constant perturbation, switched on at time The integrals (37.17) become straightforward, and we obtain .0=t ( ) ( ) ( )1ini tnin in Va t e n iωω −= − ≠= (37.18) ( ) tVita iii =−=1 Substituting Eqs.(37.18) into Eq.(37.6) gives, to a first approximation, the wave function of the atomic system as Vt e t e tωω − − ≠ Ψ = Ψ + − Ψ∑= = (37.19) The probability (37.15) of observing the system in the state at time t, for the coefficients given by Eq.(37.18), reduces to 0 nΨ( )tan ( ) ( 2/sin4 222 2 t V ni in ωω== ) (37.20) which means that transitions from state to states only take place if the matrix elements do not vanish. The plot of niV ( )tPin as a function of inω , given in Figure 37.1 for a perturbation which is on for a time t, suggests that the probability behaves like a Dirac δ -function as t approaches infinity. We may represent the δ -function as ( ) dxe t t 2 1lim 2/ 2/sin lim ωππω ω ( ) ( ininxi dxe in ωδωδπ ω 22/2 1 2/ === ∫ ∞ ∞− ) (37.21) where use was made of a property derived from the normalization condition, written as ( ) ( ) ( ) ( ) ( )u k kukudkuduu δδδδ 1or1 === ∫∫ ∞ P t( ) ω4π6π t2π in t-t-t 2π 4π t 6π t0 Figure 37.1. Dependence of the transition probability on frequency It follows from Figure 37.1 that, in the large-t limit, we have ,0≅inω and hence ( )2sin / 2 / 1.in int tω ω⎡ →⎣ ⎤⎦ Thus, one obtains ( ) ( ) ( ) ( ) (2 24sin / 2 sin / 2 sin / 2lim lim / 2 2/ 2 / 2in in in in int t in inin t t t tt ω ω ω )π πδ ω πδ ωω πωω→∞ →∞ ⎡ ⎤= =⎢ ⎥⎣ ⎦ = so that the transition probability becomes ( ) ( ) (2 2 0 022 2lim in ni in ni i nt t tP t V Vπ π )δ ω δ ε→∞ = = == ε− (37.23) It follows that the transitions take place between states of equal unperturbed energies The transition probability is proportional to the time interval t during which the perturbation is on, that is .00 in εε → ( )tPin approaches infinity as .∞→t Since no experiment lasts for an infinite time, it is the transition probability per unit time, called the transition rate , which is of particular interest. Normally, is part of a continuum, and hence, the transition might end in any state which belongs to a finite range of N final states, rather than in a particular state. We may then define the transition rate as ( )dNtP t P intni ∫∞→→ = 1lim (37.24) The integral over the final states is usually transformed into one over energy, if we define a density of states ( ) ,ρ ε representing the number of continuum states per energy interval, by taking ( )0ndN d 0nρ ε ε= (37.25) so that, substituting Eqs.(37.23) and (37.25), Eq.(37.24) gives ( ) ( ) ( ) ( )20 0 0 0 01 2limi n in n n ni n i ntP P t d Vt πρ ε ε ρ ε δ ε ε→ →∞= =∫ = − (37.26) This result is known as Fermi's golden rule, which states that transitions may occur only between states of equal energies for which the matrix elements of the perturbation operator do not vanish, and that the transition rate is proportional to both the square modulus of these matrix elements and the density of final states. 37.3. EMISSION AND ABSORPTION OF RADIATION Consider the transitions between stationary states which are induced by a harmonic perturbation of the form ( ) ( ) ( ) ( ) ( )( )titi eeArVtArVtV ωωωωω −+== GG ˆcosˆ2ˆ (37.27) It is assumed that the harmonic perturbation corresponds to the interaction of either the electric or magnetic field components of the incoming radiation with the electric or magnetic moment of the atom. Thus, the coupling between the system and the perturbing field can be taken in the form of a field amplitude ( )ωA times a displacement of the system ( ).ˆ rV G On substitution of Eq.(37.27) into Eq.(37.10) one obtains ( ) ( ) ( )( ) ( )( )titinititiinni eeAVeeArVtV ωωωω ωω −− +=+ΨΨ= 00 ˆ G (37.28) It follows from Eq.(37.17) that n ni ia t V A e e dtω ω ω ωω ′ ′− − − +⎡ ⎤ ′= − +⎣ ⎦∫= (37.29) inin eeAV 0 ⎥⎦ ⎤⎢⎣ ⎡ ++−= ωωωω ω ωωωω V A e eω ω ω ωω ω ω ω ω − − − +⎡ ⎤− −= +⎢ ⎥− +⎢ ⎥⎣ ⎦= If the atomic system is bathed into a radiation field of frequency ,inni ωωω −== which implies that according to the Bohr condition (37.16), the transition from state to state describes a process of induced absorption, where the energy of the system is increased by energy transfer from the radiation field to the atom. If 00 in εε > ,ni inω ω ω= = − the second term on the right-hand side of Eq.(37.29) grows without limit, so that the first term can be neglected.