Chronological Table of Atomic and Molecular Physics Development

Chronological Table
for the Development of Atomic and Molecular Physics
≈ 440 Empedocles assumes, that the whole world is constant proportions”: Each chemical element
BC composed of 4 basic elements: Fire, Water, Air consists of equal atoms which form with sim-
and Soil. ple number ratios molecules as building blocks
≈ 400 Leucippos and his disciple Democritus claim, of chemical compounds.
BC that the world consists of small indivisible 1811 Amedeo Avogadro derives from the laws
particles, called atoms, which are stable and of Gay-Lussac (∆ p/ p = ∆T/T ) and Boyle-
nondestructable. Marriot ( p · V = constant for T = constant) the
≈ 360 Plato attributes four regular regular geometric conclusion that all gases contain under equal
BC structures composed of triangles and squa- conditions (pressure and temperature) the same
res (Platonic bodies) to the four elements and number of particles per volume.
postulates that these structures and their inter- 1857 Rudolf J.E. Clausius develops further the
change represent the real building blocks of the kinetic gas theory, founded by D. Bernoulli.
world. 1860 Gustav Robert Kirchhoff and Robert Bunsen
≈ 340 Aristotle contradicts the atomic theory and as- create the foundations of spectral analysis of
BC sumes that the mater is continuous and does the chemical elements.
not consist of particles. 1865 Joseph Lohschmidt calculates the absolute
300 Epicurus revives the atomic model and assu- number of molecules contained in 1 cm3 of
BC mes that the atoms have weight and spatial a gas under normal conditions ( p = 1 atm,
extension. T = 300 K).
200 BC no real progress in atomic physics. 1869 Lothar Meyer and D.I. Mendelejew esta-
–1600 AC blish (independent of each other) the Periodic
1661 Robert Boyle fights in his book: “The Sceptical System of the Elements.
Chemist” for the atomic model, which states, 1869 Johann Wilhelm Hittorf discovers the cathode
that all matter consists of atoms which dif- rays in gas discharges.
fer in size and form for the different elements. 1870 James Clark Maxwell gives the mathematical
He defines the terms “chemical element” and foundations to the kinetic gas theory. He defi-
“chemical compound”. nes the atoms as “absolute and unchangeable
1738 Daniel Bernoulli assumes that heat can be ex- building blocks of matter”.
plained as the movement of small particles. He 1884 Ludwig Boltzmann develops from statistical
may be regarded as the father of the kinetic gas grounds the distribution function for the energy
theory. of a system of free atoms in a constant volume.
1808 John Dalton supports in his book “A New Together with the Austrian physicist Josef Ste-
System of Chemical Philosophy” the atomic fan he derives the Stefan–Boltzmann radiation
hypothesis by describing his experiments on law.
careful weighing the masses of reactants and 1885 Johann Jakob Balmer finds the Balmer-
reaction products of a chemical reaction. The formula for the spectral lines of the hydrogen
results of these experiments lead to the “law of atom.
504 Chronological Table
1886 Eugen Goldstein discovers the “Kanal- 1913 Niels Bohr (Nobelprize 1922) develops his new
Strahlen” (anode rays). atomic model, based on the Rutherford model
1886 Heinrich Hertz detects experimentally the elec- and the quantum hypothesis of Planck.
tromagnetic waves predicted by Maxwell’s 1913 Henry Moseley finds periodic regularities for
theory and discovers 1887 the photo-electric the absorption frequencies of X-rays by diffe-
effect and performs first experiments on the rent atoms and is able to determine the nuclear
absorption of cathode rays. charge number Z of the atoms from his mea-
1888 Phillip Lenard further investigates the absorp- surements of absorption edges.
tion of the cathode rays James Franck and Gustav L. Hertz investigate
1895 Wilhelm Conrad Röntgen discovers, while wor- the inelastic collisions of electrons with atoms
king on the properties of cathode rays a new (Franck–Hertz experiment). Nobel prize 1925.
kind of radiation which he called X-rays (first 1919 Arnold Sommerfeld comprises all known facts
Nobel Prize in Physics 1901). and models of atoms in his famous textbook:
1896 Henry Becquerel first discovers radioactivity “Atombau und Spektrallinien” and refines the
(Nobel prize 1903). atomic model of Bohr.
1898 Marie Curie separates different radioactive ele- 1921 Otto Stern and Walter Gerlach investigate
ments (Polonium and Radium) from minerals the deflection of atoms in an inhomogeneous
(Nobel prizes for Physics 1903 and Chemistry magnetic field and demonstrate the quantiza-
1911). tion of the component of the atomic angular
1900 Max Planck presents his new theory of black momentum.
body radiation, introducing the energy quanta 1923 Arthur Holly Compton (Nobel prize 1927) ex-
h · ν of the radiation field. This is nowadays plains the inelastic scattering of X-rays by
regarded as the birth year of quantum physics electrons (Compton effect) using the model of
(Nobel prize 1918). light quanta.
1905 Albert Einstein develops his theory of Brow- 1924 Louis de Broglie (Nobel prize 1929) introduces
nian motion. He explains the photoelectric the concept of matter waves.
effect using Planck’s light quantum hypothesis 1925 S.A. Goudsmit and G.E. Uhlenbeck explain
(Nobel prize 1921). the anomalous Zeeman effect by introducing
1906 Charles Glover Barkla discovers the charac- the electron spin, postulated theoretical already
teristic X-rays of the elements (Nobel prize 1924 by W. Pauli.
1917). 1925 W. Pauli (Nobel prize 1945) introduces the ex-
1909 Robert Millikan measures the elementary clusion principle (Pauli-principle) which states
charge e with his oil-droplet experiment (Nobel that every existing atomic state occupied by
prize 1923). more than on electron must be described by
1911 Ernest Rutherford and his coworkers inve- a wavefunction (product of spatial part and spin
stigate the scattering of α-particles by gold function) which is antisymmetric with respect
nuclei and postulates his atomic model. This to the exchange of two electrons.
can be regarded as the foundation of modern 1925 Erwin Schrödinger (Nobel prize 1933) extends
atomic physics (Nobel prize for Chemistry the ideas of deBroglie about matter waves to
1908). a general wave-mechanics which is based on
1912 Max von Laue (Nobelprize 1914) and his co- a special wave equation, called the Schrödinger
workers demonstrate, that X-rays represent equation.
electro-magnetic waves by observing the dif- 1927 Wolfgang Pauli gives a mathematical descrip-
fraction of X-rays by crystals. tion of the electron spin in form of quadratic
Shortly later William Henry Bragg (Nobelprize “spin-matrices” with two rows and two co-
1915) confirms this result and furthermore lumns. Werner Heisenberg (Nobel prize 1932)
shows that both the characteristic and the develops together with Max Born (Nobel prize
continuum radiation could be polarized. 1954) and Pascual Jordan the mathematical
Chronological Table 505
concept of quantum mechanics, represented by rimental verification of the NH3 -maser by J.P.
matrices. He derives the uncertainty relations. Gordon, H.J. Zeiger and Ch. Townes.
1928 J.C. Davisson (Nobel prize 1937) and L.H. 1957 Explanation of supra-conductivity by John
Germer prove experimentally the wave nature Bardeen, Leon Cooper and J. Robert Schrieffer
of electrons by observing the diffraction pattern (BCS theory) Nobel prize 1972.
of electrons passing through thin crystalline 1958 Rudolf Mößbauer: Recoil-free emission and
foils. absorption of γ -quants by atomic nuclei
Paul Dirac (Nobel prize 1933) develops a re- (Mößbauer effect) (Nobel prize 1972).
lativistic theory of Quantum Mechanics. 1959 Arthur Schawlow (Nobel prize 1995) and
Chandrasekhara Venkata Raman (Nobel prize Charles Townes give detailed description for
1930) discovers the inelastic scattering of light the extension of the maser principle to the
by molecules (Raman-effect). optical range.
1932 E. Ruska (Nobel prize 1986) constructs the first 1960 First experimental realization of an optical
electron microscope. maser (ruby laser) by Th. Maiman.
1936 I. Rabi (Nobel prize 1944) demonstrates a new 1961 The first He-Ne-laser is constructed by W.R.
techniques of radiofrequency spectroscopy in Bennet and A. Javan, based on detailed inve-
molecular beams for the precise measurement stigations of atomic collision processes in gas
of magnet moments. discharges.
1944 G.Th. Seaborg (Nobelprize for Chemistry 1966 The dyelaser is developed indepently by F.P.
1951) identifies the first tran-uranium ele- Schäfer and P.A. Sorokin.
ments. 1971 G. Herzberg receives the Nobel prize in Che-
1947 Polykarp Kusch (Nobel prize 1955): Measure- mistry for his centennial work on molecular
ment of the magnetic moment of the electron. spectroscopy.
Willis Lamb (Nobel prize 1955): Measurement 1980 First proposals for optical cooling of atoms by
of the energy difference (Lamb-shift) between photon recoil by Th.W. Hänsch, A. Schawlow
the 2S1/2 and 2P1/2 levels in the hydrogen atom. and V. Letokhov.
1947 John Bardeen develops together with W.H. Br- 1982 Development of tunnel microscopy by G. Bin-
attain and W. Shockley the transistor (Nobel ning and H. Rohrer, where single atoms on
prize 1956). surfaces can be observed (Nobel prize 1986).
1948 Felix Bloch and Edward Mills Purcell (Nobel 1986 Discovery of high temperature supra conduc-
prize 1952) demonstrate the nuclear magnetic tivity by J. Bednarz and K.A. Müller (Nobel
resonance technique NMR. prize 1986).
1948 J. Schwinger, R.P. Feynman and S. Tomonaga 1988 Nobel prize to H. Michel, J. Deisenhofer and
(Nobel prize 1965) Theoretical formulation of R. Huber for the elucidation of the primary
quantum field theory (quantum Electrodyna- process in the photosynthesis of green plants
mics). using femtosecond laser spectroscopy.
1950 A. Kastler (Nobel prize 1966) and J. Brossel 1989 Nobel prize to Norman Ramsey, H. Dehmelt
demonstrate the experimental technique of op- and Wolfgang Paul for the experimental storage
tical pumping using incoherent light sources and trapping of neutrons, ions and electrons in
before the invention of the laser. electromagnetic traps.
1953 F.H. Crick and J.D. Watson prove experimen- 1991 Pulse-Fourier-transform NMR spectroscopy:
tally by X-ray diffraction the double helix Nobel prize to Richard Ernst.
structure of DNA (Nobel prize for medicine 1992 Manipulation of single atoms on surfaces using
1963). the atomic force microscope.
1954 N.G. Basow, A.M. Prochorov and Ch. Tow- 1994 Optical cooling of free atoms in the gas phase;
nes (Nobel prize 1964) develop the theoretical observation of optical molasses.
foundations of the maser principle, based on 1995 Realization of magneto-optical traps; cooling
Kastler‘s idea of optical pumping. First expe- of atoms below 1 µK by Sysiphos cooling,
506 Chronological Table
developed by C. Cohen-Tannoudji and cowor- 1998 First demonstration of a continuous coherent

kers. beam of cold atoms from a BEC (atom laser)
First realization of Bose–Einstein Condensa- by Th.W. Hänsch and coworkers.
tion (BEC) by C. Wieman, E. Cornell and inde- 2001 Production of very cold molecules by recom-
pently by W. Ketterle, using the combination of bination of atoms in a BEC.
optical cooling and evaporation cooling to reach 2005 First observation of Bose Einstein Condensa-
temperatures below 100 nK (Nobel prize 2001). tion of molecules.
Solutions to the Exercises
Chapter 2 10−3
b) 1 cm3 He =
ˆ VM
22.4
1. a) The mean distance is
6 ×1023 × 10−3
1 ⇒ N= = 2.7 ×1019 .
d= 3 m 22.4
2.6 ×1025
= 3 ×10−9 m ≈ 15 atom diameters . 6 ×1023
c) 1 kg N2 =
ˆ × 103 molecules
28
b) The filling factor η is:
⇒ N = 4.3 ×1025 atoms .
4 4
η= πR3 n = π 10−30 × 2.6 ×1025 d) 10 dm3 H2 at 106 Pa =
ˆ 100 dm3 at 105 Pa =
3 3
= 1.1 ×10−4 = 0.01% . 1 atm
100
c) The mean free path length is ⇒ ν= ≈ 4.5 moles
22.4
1 ⇒ N = 4.5 × 6 ×1023 = 2.7 ×1024 molecules =
Λ= √ 5.4 ×1024 H-atoms .
nσ 2
σ = π(2r)2 = 4πR2 = 1.3 ×10−19 m2
4. p = nkT ; n = 1 cm−3 = 106 m−3
n = 2.6 ×1025 m−3
1 ⇒ p = 106 × 1.38 ×10−23 × 10 [Pa]
⇒ Λ= √ m = 2.2 ×10−7 m
2 × 3.3 ×106 = 1.38 ×10−16 Pa ≈ 1.38 ×10−18 mbar .
= 220 nm .
Such low pressures cannot be obtained in laborato-
2. The mass density is: ries. Because of outgassing of the walls of a vacuum
chamber and backstreaming of gas through the va-
m = (0.78 × 28 + 0.21 × 32 + 0.01 × 40) cuum pump the lowest achievable pressure in the
lab is around 10−10 Pa ≈ 10−12 mbar.
× nAMU
5. 100 ◦ N =ˆ 273 K ⇒ 1 ◦ N = ˆ 2.73 K. The mean en-
1 AMU = 1.66 ×10−27 kg, n = 2.6 ×1025 /m3 ergy per atom and degree of freedom for a fixed
⇒ m = (21.8 + 6.72 + 0.4) temperature must be independent on the chosen
temperature scale. The new Boltzmann constant kN
× 2.6 ×1025 × 1.66 ×10−27 kg/m3
is then obtained from:
= 1.25 kg/m3
1 1
1 ⇒ kB TK = kN TN
3. a) 1 g12 C = mol 2 2
12 1
⇒ kN = kB = 5.1 ×10−24 J/◦ N .
⇒ N = 6 ×1023 /12 = 5 ×1022 . 2.73
508 Solutions to the Exercises
The boiling point of water, measured in the new The vertical distribution is
temperature scale is: ∗
n(z) = n 0 e−m gz/kT

100 ◦ n(h 1 )
= e−(m g/kT )(h 1 −h 2 )
∗
TS = 100 + N = 136.6 ◦ N . ⇒
2.73 n(h 2 )
m ∗ g∆h
6. The sound velocity vPh in a gas at pressure p and ⇒k=
density is T ln(n 1 /n 2 )
7.7 ×10−18 × 9.81 × 6 ×10−5
=
vPh = κ p/ with κ = C p /C V 290 ln(49/14)
f +2 = 1.25 ×10−23 J/K .
= ,
f The best value accepted today is
where C p is the molar specific heat at constant pres- k = 1.38 ×10−23 J/K .
sure, C V at constant volume and f is the number
8.3
of degrees of freedom. NA = R/k =
1.25 ×10−23 mol
⇒ vPh
2
= κ p/ . ≈ 6.02 ×1023 /mol
M = NA m = 6.02 ×1023 × 4.76 ×10−14 g/mol
From the general gas equation for a mole
volume VM = 3 ×1010 g/mol .
pVM pM When a colloid molecule has an average mass num-

pVM = RT ⇒ R = = , ber of 104 AMU the nanoparticle consists of about
T T
3 ×106 molecules.
(M = mole mass) 8. a) If the first diffraction order is at an angle β1 =
87◦ , the incidence angle α can be obtained from the
we obatain:
grating equation (see Fig. S.1):
vPh
2
= κRT/M . d(sin α − sin β1 ) = λ ⇒
λ
For radial acoustic resonances the acoustic sin α = + sin β1
wavelength is d
5 ×10−10
= + 0.99863
nλ = r0 ⇒ vPh = νn λ = (νn /n)r0 0.83 ×10−6
= 0.99923
The general gas constant R is then obtained as
⇒ α = 87.75◦ .
vPh
2
M ν2r 2 M The second diffraction order appears at:
R= = n2 0
κT n κT
2λ
For argon κ = ( f + 2)/ f = 5/3, M = 40 g/mole. sin β2 = sin α − = 0.99803 ⇒ β2 = 86.40◦ .
d
Measuring the frequencies νn for different values The difference is ∆β = 0.6◦ . For α = 88.94◦ we
of the integers n (n = 1, 2, 3, . . . ) yields the gas would obtain: ∆β = 0.75◦ .
constant R, because M, r0 , κ, T are known.
7. The effective mass of the collodial particle is:
4 3 4
m∗ = m − πr liquid = πr 3 (part − liquid )
3 3
= 7.74 ×10−18 kg,
m = 4.0 ×10−17 kg . Fig. S.1.
Chapter 2 509
The radius r0 of the spheres is (according to

Sect. 2.4.3)
1√
r0 = 2a = 2.33 ×10−10 m
4
4
⇒ Vsph = πr03 = 5.3 ×10−29 m3 .
3
The filling factor is
√
4 × 43 πr03 16π × 2 2
η= = ≈ 0.78 .
a3 3.64
9. The van der Waals equation for 1 mole is:

Fig. S.2. a
p + 2 (VM − b) = RT
VM
(VM = mole volume).
b) The Bragg condition is
a ab
2d sin α = λ ⇒ pVM − pb + − = RT .
VM VM2

λ 2 ×10−10 b a/ p ab/ p
⇒ d= = m ⇒ pVM 1 − + 2 − 3 = RT .
2 sin α 2 × 0.358 VM VM VM
= 2.79 ×10−10 m .
This can be written as
This is half the side length a of the elementary cell
of the cubic crystal (Fig. S.2). pVM (1 − x) = RT with (x 1) .
⇒ a = 0.56 nm . With
NaCl has a face-centered cubic (fcc) crystal struc- 1
≈ 1+x
ture. Each elementary cell is occupied by four NaCl 1−x
molecules. The molecular mass of NaCl is (23 + b a/ p ab/ p
⇒ pVM = RT 1+ − 2 + 3 .
35) = 58 AMU. The number of molecules per m3 VM VM VM
is:
4 Comparison with the virial equation (vires =
N= m3 = 2.5 ×1028 m−3 , forces)
5.63 × 10−30
The mass of one molecule NaCl is: B(T ) C(T )
pVM = RT 1 + + 2
2.1 ×103 VM VM
m NaCl = = kg = 9.2 ×10−26 kg .
N 2.28 ×1028 gives the coefficients:
In 1 mole of NaCl (= 58 g) are NA molecules. B(T ) = b = 4 times the eigenvolume of all
5.8 ×10−2 molecules in VM , and
⇒ NA = mole−1 = 6.3 ×1023 mole−1 . a
9.2 ×10−26 C(T ) = − ,
c) From the Bragg condition p
2d sin ϑ = mλ The ratio pi = a/VM2 is called the “internal pressu-

re” = pressure caused by the mutual attraction of
we obtain for m = 1 the side length a = 2d of the the molecules. The term C(T )/VM2 gives the ratio
elementary cell of the fcc crystal as pi / p of “internal pressure” to external pressure.
λ 10. a) If a parallel beam of atoms A per m2 per s
a= = 6.6 ×10−10 m .
sin ϑ hits atoms B at rest, the scattering cross section is
Fig. S.3. With an acceleration voltage U the velocity vz is

from
m
eU = v2z ⇒ vz = 2eU/m . (2)
2
Inserting in (1) gives
2πm 4π 2 m 2 2eU
L= vz ⇒ L 2 = 2 2
eB e B m
e 8π 2 U
(Fig. S.3) σ = π(r1 +r2 )2 . For equal atoms (A = B) = 2 2,
m L B
r1 = r2 ⇒ σ = 4πr 2 = πD2 with D = 2r. % % % % % %
δ(e/m) %% 2δ L %% %% 2δ B %% %% δU %%
The number of particles scattered out of the beam ⇒ ≤% + +
e/m L % % B % %U %
along the path dx through a gas of atoms B with
density n B is = 4 ×10−3 + 2 ×10−4 + 1 ×10−4
= 4.3 ×10−3 .
dN = −Nn B σ dx
⇒ N(x) = N0 e−n B σx . In order to set L = 4 f one has to determine
The mean free path length for which N(x) = N0 / e the focal length f . This is achieved by shifting
is the aperture A2 until maximum transmission is
1 reached.
Λ= .
nBσ Assume the maximum deviation of the electrons
b) In a gas with thermal equilibrium the particles from the axis is a = 5 mm;
have an isotropic Maxwellian velocity distribution.
The mean time between two collisions is: with L = 100 mm we obtain
1 5
τ= ⇒ sin α ≈ = 0.2 rad
nσ|vr | 25
where the relative velocity is (Fig. S.4). If the position of the focus is shif-
ted by ∆L from its optimum value, the radius
vr = v1 − v2
of the convergent electron beam is enlarged by
⇒ vr2 = v12 + v22 − 2v1 · v2 ∆L tan α from r0 to r0 + ∆L tan α. If the cur-

⇒ vr2 = v12 + v22 , because v1 · v2 = 0 rent I of electrons flows through the aparture
with radius r0 = 0.5 mm (can be measured within
for A = B is v12 = v22 = v2
∆I/I = 10−3 ) the shift can be seen, if the area of
⇒ vr2 = 2 v2 .
1
⇒ τ=√ ,
2 nσ v2

Λ = τ v2
1
=√ .
2 nσ
11. a) For a longitudinal magnetic field B with
a length L = 4 f , the time of flight between the
two aperatures in Fig. 2.67 is, according to (2.99b),
2πm
T= with T = L/vz . (1)
eB Fig. S.4.
Chapter 2 511

the aparture has increased to πr02 1 + 10−3 . 12. a) The vertical force is gravitation. If the flight
* + direction is the x-direction the flight time is:
π (r0 + ∆r)2 − r02 ≤ 10−3 πr02
L 2
⇒ ∆r 10−3r0 = 2.5 ×10−4 mm , tf = = s = 6.7 ×10−3 s .
v 300
∆r = ∆L tan α
The vertical deflection is
⇒ ∆L ≤ 2.5 ×10−4 mm/0.2 1 1
= 1.25 ×10−3 mm , ∆1 z = gt 2 = · 9.81 · 6.72 · 10−6 m
2 2
⇒ ∆L/L = 1.25 ×10−5 . = 2.2 ×10−4 m = 0.22 mm .
The geometrical uncertainty of ∆L from the measu- The divergence of the beam is:
rement of L is therefore much larger than that of the
b1 + d0 4 ×10−6
uncertainty of measuring the transmitted current. ∆ϑ = = = 2 ×10−5 .
The maximum relative error is therefore not affec- 2· L 2
ted by the uncertainty of optimising the transmitted The width of the beam at a distance d2 = 200 cm
current but rather by the mechanical accuracy of downstream of S1 is:
length measurement. ∆2 z = d2 · ∆ϑ = 4 ×10−3 m .
b) The maximum deflection from the straight path
is δ x < 10−3 b, because the current I ∝ b can be The deflection by gravity therefore changes the
measured within ∆I/I = 10−3 . The deviation from beam intensity, transmitted through a slit S2 by the
the z-axis is fraction 2.2 ×10−4 /4 ×10−3 = 5.5 ×10−2 = 5.5%.
1 1 1 b) The deflection of atoms with mass M and charge
x = a t 2 with a = eE x − evB y = Fx . ∆q is:
2 m m
With t = L/v and v2 = 2eU/m we obtain 1 E · ∆q 2
2
∆z = t
1 L 2 M
x= Fx 1
2m 2eU = · 5 ×106 · ∆q · 6.72 × 10−6 m
∂x ∂x ∂x 2
⇒ δx = δ Fx + δL + δU ∆q
∂Fx ∂L ∂U = 1.1 ×102 · [m] .
% % % % % % % % M
% δ x % % δ Fx % % % % %
⇒ %% %% = %% % + 2 % δ L % + % δU % . Assume M = 4 AMU = 6.7 ×10−27 kg (He-atoms)
x F % % L % % U %
x and a sensitivity of ∆z min = 10 µm than the mini-
With δ L/L = 1.25 ×10−5 , δ Fx /Fx = δ E x /E x + mum value of ∆q is ∆qmin = 6 ×10−35 C = 3.8 ×
δ B y /B y = 2 ×10−4 , δU/U = 10−4 we get 10−16 e.
δx c) The change ∆z of the deflection is 2∆z = 2.2 ×
= 3.3 ×10−4 102 ∆q/M [m]. The relative change of the intensity,
x
transmitted through S2 is, according to a)
⇒ δ x = 3.3 ×10−5 mm
∆I 2.2 ×102 ∆q/M
for x = b = 0.1 mm. The uncertainty δ x < 10−3 b = .
I 4 ×10−3
= 1 ×10−4 mm due to the uncertainty of measuring
the current I is larger here than in problem a) be- If a relative change of 10−4 can be still measured,
cause of the uncertainties of measuring E, B and U. than the minimum charge difference
The ratio e/m = E 2 /(2UB 2 ) can then be measured 10−4 × 4 ×10−3
within ∆q = ·M
% % % % % % 2.2 ×102
δ(e/m) % δ E % % δU % %δ B%
%
= 2% %+% % % % + 2 %% %%
e/m E U % B can be measured. Inserting M = 6.7 ×10−27 kg
% % gives
% δx %
≤ %% %% < 10−3 .
x ∆q = 1.2 ×10−35 C .
13. From mv2 /R = evB and f 0 = R/ sin ϕ one obtains The optimum voltage is then:

mv mv 1 √ R1 + R2 m 2 R2
B= = = 2meU . U = φ2 − φ1 = v0 ln
eR e f 0 sin ϕ e f 0 sin ϕ 2R0 e R1

mv02 R2
With eU = 103 eV = 1.6 ×10−16 J, m = 40√AMU = = ln
e R1
40 × 1.66 ×10−27 kg, sin ϕ = sin 60◦ = 12 3, f 0 =
2eV0
0.8 m ⇒ B = 4.2 ×10−2 Tesla. = ln(R2 /R1 ) .
14. According to (2.100) the focal length f is: e
√ √ b) Assume an ion enters the cylindrical field at
4 φ0 2 φ0 /a ϕ = 0 and r = R0 = (R1 + R2 )/2 with the velo-
f = z0 = z0
" 2a dz " city v0 . Assume it deviates at time t from its
√ dz
0 φ0 +az 2 z=0 (φ02 /a)+z 2 optimum path r = R0 by δr. The equation of motion
√ F = m · a than becomes for the radial motion:
2 φ0 /a
= %z0 v2
% mδr̈ = m · + e · E(r + δr) . (3)
ln z + (φ02 /a) + z 2 %% r
√ 0 Expansion of E into a Taylor series yields:
2 φ0 /a
= / 0. dE
z 0 + φ02 /a+z 20 E(R0 + δr) = E(R0 ) + δr + . . . . (4)
ln dr R0
φ02 /a
From a) we obtain:
15. a) The potential of the cylindric condenser can be dE U 1
= · 2. (5)
obtained from the Laplace equation ∆φ = 0, which dr ln(R2 /R1 ) r
is written in cylindric coordinates (r, ϕ, z) as: Inserting this into (4) and (3) gives:

1 ∂ ∂φ v02 2 v02 δr
r· =0, δr̈ − 3 R0 + 1− =0
r ∂r ∂r r R0 R0
with the solution 1 1 1 3
= 3 ≈ 3 − 4 δr + . . .
r3 R0 (1 + δr/R0 )3 R0 R0
φ = c1 ln r + c2 .
v02 δr δr
⇒ δr̈ − 1−3 −1+ =0
The cylinder surfaces r = R1 and r = R2 are at the R0 R0 R0
fixed potentials φ1 and φ2 . This gives: 2v2
⇒ δr̈ + 20 δr = 0 .
c2 = φ1 − c1 ln R1 R0
φ2 − φ1 With ω0 = v0 /R0 this becomes:
c1 =
ln(R2 /R1 ) δr̈ + 2ω20 δr = 0
φ2 − φ1 √
⇒ φ(r) = φ1 + · ln(r/R1 ) . ⇒ δr = R0 sin 2ω0 · t .
ln(R2 /R1 )
The electric field E(r) is:
∂φ φ1 − φ2 1
E(r) = − = · .
∂r ln(R2 /R1 ) r
The optimum path of the ions through the center
R0 = (R1 + R2 )/2 of the cylindric sector field is
obtained from:
mv02 2e φ1 − φ2
= e · E(R0 ) = .
R0 R1 + R2 ln(R2 /R1 ) Fig. S.5.
Chapter 2 513
√ √
After the time t = π/( 2ω0 ) ⇒ ϕ = π/ 2 = Two masses can be separated if their flight time
127◦ . The deviation δr becomes zero. The cylin- difference ∆T2 is at least ∆T1 or larger. The mass
drical condenser with an angle ϕ = 127◦ therefore resolution of our example is only ∆m/m ≈ 10.
acts as focussing device. It can be greatly increased by the McLaren ar-
16. An ion produced at the location x travels a distance rangement with two different accelerating electric
s = 12 at12 with a = eE/m in the electric field E = fields.
U/d to the grid 2 (Fig. S.5). b) The increase of mass resolution in the reflec-
tron can be seen as follows: Assume the lengths of
2ms the two arms of the reflectron to be L 1 = L 2 = L.
⇒ t1 =
eE Two ions, generated at two different locations have
2eEs velocities v1 and v2 with vi = (2eE · si /m)1/2 .
v1 = (eE/m) t1 = .
m Their flight time is: Ti = 2L/vi without penetra-
The drift time in the field-free region between grid 2 ting into the reflection field E r . Here they penetrate
and 3, where the ion moves with constant velocity, a distance dr determined by the energy balance:
is:
m 2
m v = e · E r · dr ⇒ dr = mvi2 / (2eE r ) .
t2 = L/v1 = L . 2 i
2eEs
The total flight time is: The deceleration time is obtained from

m 2s + L 1 Er
T = t1 + t2 = √ . dr = e t 2 .
eE 2s 2 m
The time difference ∆T for ions of equal mass,
produced at s1 = (d + b)/2 and s2 = (d − b)/2 (i.e., Their time for penetration and reflection is therefore
at the opposite edges of the ionization volume) is
t = 2 · (2dr · m/eE r )1/2 .
m 2s1 + L 2s2 + L
∆T1 = √ − √
eE 2s1 2s2 Inserting si = (d ± b)/2 we obtain for the total flight

m d +b+ L d −b+ L time of an ion through the reflectron:
= √ − √ .
eE d +b d −b
2L mvi
For m = 100 AMU = 1.66 ×10−25 kg, b = 2 mm, Ti = +2 .
d = 30 mm, L = 1 m one obtains: vi eE r
∆T1 = 1.018 ×10−5 (5.769 − 6.143)s Inserting si = (d ± b)/2 ⇒ vi = [(2eE/m)(d ±
= −3.811 µs . b)/2]1/2 .
We can calculate the maximum time difference for
The ion with s = (d + b)/2 has a shorter flight time
ions generated at si = (d ± b)/2 as:
than an ion starting from s = (d − b)/2, because it
is accelerated longer and has a larger velocity.
2L 1 1
Two ions, with masses m 1 and m 2 , both starting ∆T = √ √ −√
from the middle of the ionization volume (s = d/2) eE/m b−d b+d

have the flight time difference: 2m eE √ √
+ d −b− d +b .
d + L √ √ eE r m
∆T2 = √ m1 − m2 .
edE With d∆T/ db = 0 one obtains the optimum re-
Inserting the numerical values for m 1 = 110 AMU, tarding field E r as
m 2 = 100 AMU gives:
∆T2 = 1.49 ×108 × 2 ×10−14 s E d − b − (d 2 − b2 )1/2
Er = .
≈ 3 µs . L (d 2 − b2 )1/2 − (d − b)2 (d 2 − b2 )−1/2
c) The width of the ion beam at the exit of the sector The torque is the time derivative of the angular
field is (see Fig. 2.74a) momentum L = r × p = m · r × v
2m dL
b2 = b1 + ∆v =D.
eB dt
mv2 mv
= qvB ⇒ R = Since D = 0 ⇒ L = const.
R qB 18. a) According to (2.163a) the impact parameter is

m 2 1 2Um
v = qU ⇒ R = b=
qZe
cot(ϑ/2) , with
2 B q
4πε0 µv02
R2 B 2 q q = 2e , Z = 79 ,
⇒ m= .
2U ε0 = 8.85 ×10−12 A s/V m ,
In order to seperate two masses m 1 and m 2 , the µ 2
condition cot 45◦ = 1 , v = 5 MeV = 8 ×10−13 J
2 0
2(R1 − R2 ) ≥ b2 ⇒ b = 2.27 ×10−14 m = 22.7 Fermi .
has to be met. The mass resolution is then b) For the backwards-scattered particles (ϑ = 180◦ )
we obtain the minimum distance rmin at the turning
m R2 B 2 q 2U
= point from the energy balance
∆m 2U B 2 q R12 − R22
µ 2 qZe
R2 v =
= 2 2 0 4πε0rmin
R1 − R22
qZe
Rm ⇒ rmin = = 4.54 ×10−14 m .
≈ 2πε0 µv02
2(R1 − R2 )
with c) For ϑ = 90◦ the impact parameter is b0 = 2.27 ×
10−14 m. All particles with b < b0 are scattered into
1 the angular range 90◦ < ϑ ≤ 180◦ .
Rm = (R1 + R2 ) .
2 In order to estimate the maximum value of b (i.e.,
Since 2(R1 − R2 ) > b2 the smallest deflection angle ϑ) we assume bmax =
m Rm d/2, where d is the average distance between two
⇒ ≤ . gold atoms in the scattering gold foil. In this case
∆m b2 the α-particle passes between two gold atoms and
Assuming Rm = 0.3 m, b2 = 1 mm experiences a net deflection force of zero.
∆m The number density of gold atoms is
⇒ ≤ 300 .
m NA
nV = = 6 ×1022 /cm3
This is better than our simple TOF spectrometer, M
but worse than the reflectron. with the mass density = 19.3 g/cm3 ; the Avo-
17. The torque D on a particle with mass m is: gadro number NA = 6 ×1023 /mole and the molar
D=r×F, mass M = 197 g/mole.
The number density n F per cm2 of gold atoms in
where F is the force acting on the particle at the foil with thickness t = 5 ×10−6 m is n F = n V t =
√
a distance r from the center. 3 ×1019 /cm2 . With bmax = 12 d = 12 / n F = 9.1 ×
For centro-symmetric force fields is 10−11 cm = 9.1 ×10−13 m the scattering cross
section is
F̂ = f(r) · r̂
⇒ D = f(r) · r × r̂ = 0 . σ = πb2max ≈ 2.6 ×10−20 cm2 .
Chapter 3 515
The fraction of atoms scattered into the angular ϑ2

sin ϑ e−(ϑ/ϑ ) dϑ
2
range ϑ ≥ 90◦ is N(ϑ)∆ϑ ∝
ϑ1

◦ πb20 −14 2
N(ϑ ≥ 90 ) 2.27 ×10 ≈ ϑ e−(ϑ/ϑ ) dϑ
2
= =
N(ϑ ≤ 180◦ ) πb2max 9.1 ×10−13 # 2 $ϑ
= 6 ×10 −4
. ϑ −(ϑ/ϑ )2 2
= e
2 ϑ1
d) b(ϑ = 45◦ ) = a cot 22.5◦ = 2.71 a with a = N(1◦ ± 0.5◦ ) e−0.17 − e−1.56
⇒ = ≈ 7.5 ×105 .
qZe/(4πε0 µv02 ) ⇒ a = 2.27 ×10−14 m. N(5◦ ± 0.5◦ ) e−14 − e−21
* + This shows that the scattering rate decreases much
N(45◦ ≤ ϑ ≤ 90◦ ) π (2.41)2 a2 − a2 stronger with increasing ϑ than for the Rutherford
=
N(ϑ ≤ 180◦ ) πb2max scattering.
20. a)
4.8a 2
4.8 × 2.27 × 10−28
2
= 2 = µv02 Ze2
bmax 8 ×10−21 = ,
= 3.1 ×10−7 . 2 4πε0rmin
rmin = 5 ×10−15 m , Z = 29 ,
19. The rate N(ϑ) of particles scattered into the angular 1 × 63
µ= = 0.98 AMU
range ϑ1 ≤ ϑ ≤ ϑ2 is for Rutherford scattering: 64
µ 29 × 1.62 × 10−38
⇒ v02 = J
ϑ2 2 4π × 8.85 ×10−12 × 5 ×10−15
sin ϑ dϑ
N(ϑ)∆ϑ ∝ = 1.33 ×10−12 J
sin4 (ϑ/2) m
ϑ1 ⇒ v02 = 1.36 ×10−12 J = 8.5 MeV .
2
ϑ2
2 cos(ϑ/2)
= dϑ b) For ϑ < 180◦ is
sin3 (ϑ/2)
ϑ1 !−1/2
# $ϑ2 E pot (rmin )
2 rmin = b 1 − µ 2 .
= − . 2 v0
sin2 (ϑ/2) ϑ1
With rmin = 5 ×10−15 m ⇒ b = 1.775 ×10−15 m
This allows the calculation of the ratio Ze2
⇒ cot(ϑ/2) = b/a with a =
4πε0 µv02
N(1◦ ± 0.5◦ ) 46,689 ◦
= = 218 . ⇒ ϑ ≥ 113.4 .
N(5◦ ± 0.5◦ ) 214.4
For the Thomson model we obtain for a me-

dium scattering angle ϑ = 2 ×10−4 rad and an Chapter 3
average number m of scattering events in the gold
foil, according to the numerical value given in 1. With the de Broglie relation
Problem 2.18c: h
λdB =
p
m = n F σ = 3 ×1019 × 3 ×10−16 ≈ 104 h 6.63 ×10−34 m
√ ⇒ v= = −10
⇒ ϑ = m ϑ = 2 ×10−4 × 102 rad ≈ 1.2◦ mλ 10 × 1.67 ×10−27 s
= 2 ×10−2 rad ≈ 1.2◦ , = 3.97 ×103 m/s .
Thermal neutrons have at T = 300 K a mean ve- This equation can be only solved numerically. The
locity v = 2.2 ×103 m/s and a kinetic energy of solution is:
thermal
E kin = 40 meV. Our neutron is slightly super
thermal. Its kinetic energy is xm = 2.8215
m ⇒ νm = 2.8215 kT/h = 5.873 ×1010 s−1 · T [K] .
E kin = v2 = 1.31 ×10−20 J = 82 meV .
2
With λ = c/ν ⇒ dλ = −(c/ν2 ) dν we obtain in-
2. The average energy per mode is
stead of (3.16) for Sλ∗ the expression
E = n · hν ,
2πhc2 1
where n is the average number of photons Sλ∗ = ) −1
.
λ5 e hc/(λkT
in this mode. If Pn is the probability, that
a mode contains n photons, it follows for thermal With dSλ∗ / dλ = 0 we obtain in a similar way
equilibrium
2.88 ×10−3 [m]
−n·hν/kB T ∞
) λm = .
Pn = (
e
⇒ Pn = 1 . T [K]
n e−nhν/kB T n=0 Note, that dλ/ dν decreases with increasing fre-
Pn+1 quency ν. The distribution Sλ∗ , which gives the
⇒ = e−hν/kB T = x .
Pn radiation flux per constant interval dλ, therefore
( differs from Sν∗ which is given for constant interval
The geometrical series ∞ n=0 x has for x < 1 the
n
value dν. The maximum of Sν∗ at νm is not at νm = c/λm !

) 4. a) Energy conservation demands
1
xn = .
1 − x hν = ∆E kin
el
(1)
n
⎡ ⎤
With the relation: 1 1
= m 0 c2 ⎣ − ⎦
d ) n
)∞
x
n · xn = x · x = 1 − v22 /c2 1 − v12 /c2
n=0
dx (1 − x)2
The conservation of momentum requires:
we obtain
)∞ ) m 0 v2 m 0 v1
xn x k = − (2)
n = n · P(n) = n· ( n =
x 1−x 1 − v2 /c
2 2
1 − v12 /c2
n=0
1 h 2 ν2
= . 2 k2 =
−1
ehν/kB T c2
The mean energy per mode is then m 20 v12 m 20 v22
= + (3)
hν 1 − v12 /c2 1 − v22 /c2
E = hν/k T .
e B −1 2m 20 v1 · v2
− .
3. Differentiation of Sν∗ in (3.16) gives: 1 − v12 /c2 1 − v22 /c2
∂Sν∗ 6hν2 1 2hν3 ehν/kB T · h/kB T
= 2 hν/k T − 2 Taking the square of (1) gives:
∂ν c e B −1 c ( ehν/kB T − 1)2
⎡
=0
1 1
hν hν/kB T hν/kB T −1 h 2 ν2 = m 20 c4 ⎣ + (4)
⇒ 3− e e −1 =0. 1 − v1 /c
2 2
1 − v22 /c2
kB T
⎤
With x = hν/kB T this gives
2 ⎦
x − .
3= −x
⇒ x = 3 1 − e−x . 1 − v1 /c 1 − v22 /c2
2 2
1− e
Chapter 3 517
A comparison of (3) and (4) gives, after rearranging which should be larger than the slit width b. This
the terms: gives the condition
2 2 1/2
c − v12 c2 − v22 = c2 − v1 · v2 2Dh
b< √ .
⇒ (v1 − v2 ) = 0 ⇒ v1 = v2 2m E kin
⇒ ν = 0! For D = 1 m and E kin = 1 keV = 1.6 ×10−16 J
we obtain:
This means that photoabsorption by a free electron # $1/2
is not possible. The absorption can only take place 2 × 6.6 ×10−34
bmax = √ m
in the presence of an atom, which can compensate 2 × 9.11 ×10−31 × 1.6 ×10−16
the photon recoil. In the Compton effect the scat-
tered photon has the momentum ks = k and the = 8.81 ×10−6 m = 8.81 µm .
energy hνs < hν. 6. The radii of the Bohr orbitals are
b) The momentum of the photon is: n2
% % rn = a0 .
% pphot % = hν . Z
c a) For n = 1, Z = 1 ⇒ r1 = a0 = 5.29 ×10−11 m.
For hν = 0.1 eV = 1.6 ×10−20 J (λ = 12 µm) b) For n = 1, Z = 79 ⇒ r1 = 6.70 ×10−13 m.
The velocities of the electron are
1.6 ×10−20 J s
⇒ pphot = = 5.3 ×10−29 N s h Z
3 ×108 m v= = .
2πm ern m e a0 n 2
For hν = 2 eV (λ = 600 nm)
a) Z = 1, n = 1:
⇒ pphot = 1.07 ×10−27 N s c
⇒ v1 = 2.19 ×106 m/s = 7.3 ×10−3 c = .
For hν = 2 MeV 137
b) Z = 79, n = 1:
⇒ pphot = 1.07 ×10−21 N s
v1 = 1.73 ×108 m/s = 0.577 c .
The recoil velocity of a hydrogen atom with the
above momenta would be In case b) the relativistic effects become very large
p and have to be taken into account. We can calculate
v1 = = 3.2 ×10−2 m/s for hν = 0.1 eV , the relativistic velocity:
m / 0
p
v2 = = 6.4 ×10−1 m/s for hν = 2 eV , E kin = (m − m 0 )c = m 0 c
2 2 1
−1
m 1 − v2 /c2
p
v3 = = 6.4 ×105 m/s for hν = 2 MeV . Ry∗
m = −E n = Z 2 .
In the first case the atom would not be pushed n2
out of resonance for the Lyman α-line, for the last For n = 1 we obatain:

case it would be completely Doppler-shifted out of 2
m 0 c2
resonance. v = c 1− ,
5. The first diffraction minimum appears at the m 0 c2 + E 1
diffraction angle α with with m 0 c2 = 0.5 MeV we obtain:
λ h h 792 × 13.5
sin α = = = √ . E= eV = 0.084 MeV
b b p b 2m E kin 1

The full width between the two minima at both
0.5 2
sides of the central maximum is ⇒ v = c 1−
2Dh 0.584
B = 2D sin α = √ >b,
b 2m E kin = 0.517 c .
The relative error of the nonrelativistic calculation where m N is the mass of the nucleus.
is 1
∆v 0.06 ⇒ Ry 3 H = Ry∞
= c = 0.116 c = 11.6% . 1 + m e /m N
v 0.517 1
≈ Ry∞
c) The relativistic mass increase is 1 + 3·1836
1
/ 0
1 = 0.999818Ry∞
∆m = m − m 0 = m 0 −1 = 1.0971738 ×107 m−1 .
1 − v2 /c2

1 The wavelength of Lyman α n = 2 → n = 1 is then:
= m0 √ −1
1 − 0.5172 4
= 0.17 m 0 . λ= = 1.215 ×10−7 m = 121.5 nm .
3Ry
The relativistic energy correction is (see Sect. 5.4) b) For positronium (e+ e− )
∆E r (n = 1, Z = 1) = 9 ×10−4 eV . 1
µ = m e /2 ⇒ Ry( e− e+ ) = Ry∞
2
For Z = 79 it is ⇒ λ = 243.0 nm .
∆E r (n = 1, Z = 79) = 5.6 eV . 9. At room temperature (T = 300 K) only the ground

state is populated. Therefore all absorbing transi-
7. After the mean life time τ the number of neutrons tions start from the ground state with n = 1. The
have decayed to 1/ e of the initial value and after photon energies are then
the time τ ln 2 to 1/2 of the initial value. During
1
this time they travel a distance x = vτ ln 2. hνn = a 1 − 2
The velocity of the neutrons is n

1
h hτ ln 2 hνn+1 = a 1 −
v= ⇒ x= (n + 1)2
mλ mλ
6.62 ×10−34 × 900 × 0.69 with λ = c/ν we obtain
= = 2.4 ×105 m .
1.67 ×10−27 × 10−9 λ1 νn+1 1 − 1/(n + 1)2
= = .
The decay time of the neutrons could be measured λ2 νn 1 − 1/n 2
by trapping them in a magnetic quadrupole trap With λ1 = 97.5 nm, λ2 = 102.8 nm ⇒ λ1 /λ2 =
with the geometry of a circle. With a radius r = 1 m, 0.948. For n = 2 ⇒ λ1 /λ2 = 0.843, for n = 3 ⇒
they travel (2.4 ×105 /2π) = 4 ×104 times around λ1 /λ2 = 0.948.
the circle before they decay, if no other losses are The two lines therefore belong to n = 3 and n = 4.
present. The constant a can be determined from
8. The wavelength of the Lyman α-line can be
obtained from the relation c a 1
νn = = 1− 2
λn h n
hc ∗ 1
hν = = Ry 1 − with λ3 = 102.8 nm we obtain
λ 4
4 hc 1
⇒ λ= with Ry = Ry∗ /hc . a=
3 Ry λ3 1 − 1/32
hc 9
a) = · = 2.177 ×10−18 J = Ry∗ .
λ3 8
µ memN The lines therefore belong to transitions in the
Ry 3 H = Ry∞ · with µ = ,
me me + mN hydrogen atom with Z = 1, n = 3 and n = 4.
Chapter 4 519
10. Since the resolving power of the spectrograph is The total energy is then
assumed to be
% % 2 2e2
% λ % %% ν %% E≥ − .
% %
% ∆λ % = % ∆ν % = 5 ×10
5 2ma2 4πεa
From the condition dE/ da = 0 for the minimum
the difference ∆ν of two adjacent lines in the energy we obtain
Balmer spectrum has to be ∆ν ≥ ν/(5 ×105 ). The
frequencies of the Balmer series are 2πε0 2 a0
amin = =
me 2 2
Ry∗ 1 1
νn = − n ≥ 3. 4e2
h 22 n 2 ⇒ E pot (amin ) = −
4πε0 a0
The ratio ν/∆ν is then
= −4E pot (H, n = 1)
ν νn
1
4 − n12
= = ≤ 5 ×10 5
= −108 eV ,
∆ν νn+1 − νn 1
− (n+1)
1
n2 2
1
n2 − 4 E kin = − E pot = +54 eV .
⇒ n 2 ≤ 5 ×10
5 2
4 − 4 n+1
⇒ n ≤ 158 .
Chapter 4
Another way of solving this problem is as follows:

Ry∗ 1 1 1. Inserting the ansatz ψ (r, t) = g(t) · f(r) into the
ν(n) = − .
h 4 n2 time-dependent Schrödinger equation (4.7b) one
For large n we can regard ν(n) as a continuous obtains, after division by f(r) · g(t),
function of n and obtain by differentiating: 1 ∂g(t) 2 1
∗ i =− ∆ f(r) = C .
dν 2Ry 1 g(t) ∂t 2m f(r)
=
dn h n3 Since the left side of this equation depends solely
2Ry∗ 1
⇒ ∆ν ≈ ∆n on t, the right side solely on r, both sides have to
h n3 be constant, which we name C. The right side gives
with ∆n = 1 we get: the time-independent Schrödinger equation (4.6)
for C = E − E pot . Then the left side becomes
ν 1 1 1
= − 2 n3 .
∆ν 2 4 n ∂g(t) E − E pot
= g(t)
Since n 4:
2 ∂t i
−iE kin / ·t
⇒ g(t) = g0 e .
n3
≤ 5 ×105 ⇒ n 3 ≤ 4 ×106 For a free particle E pot = 0 ⇒ E kin = E. The
8
⇒ n ≤ 158 . function g(t) then represents the phase factor
11. For the uncertainty ∆r = a the kinetic energy of g(t) = g0 e−i(E/ )t

= g0 e−iωt
the electron is
with E = ω.
2 2. The reflectivity R = 1 − T can be derived
E kin ≥ .
2ma2 from (4.26a) when we insert:
Its potential energy at a distance a from the nucleus E 0.4
is = = 0.8 ,
E0 0.5
2e2 1
E pot = − . α= 2m(E 0 − E)
4πε0 a
√
2 1.67 ×10−27 × 0.1 × 1.6 ×10−22 −1 4. With
= m
1.05 ×10−34 ψ1 = A eik1 x + B e−ik1 x ,
−1
= 2.2 ×10 m 9
ψ2 = C eik2 x + D e−ik2 x ,
with a = 1 ×10−9 m ⇒ α · a = 2.2. ψ3 = A eik1 x
1/2
0.2 k1 = 2m E/2 ,
⇒ T= = 0.126 , 1/2
0.2 + 0.3125 × sinh2 (2.20) k2 = 2m(E − E 0 )/2 = iα
we obtain from the boundary condition (4.25) the
i.e., 12.6% of all particles are transmitted, 87.4% relations:
are reflected.
A+ B = C+ D,
3. For the negative potential step the same derivation
can be used as for the positive step. The reflection Ce + D e−ik2 a = A eik1 a ,
ik2 a
coefficient is k1 (A − B) = k2 (C − D) ,
% % ik a
|B|2 %% k − k %%2 k2 C e − D e−ik2 a = k1 A e−ik1 a .
2
R= = .
|A|2 % k + k % This set of equations yields the results:
# $
We abbreviate: k12 + k22
A = cos k2 a − i sin k2 a eik1 a A ,
1√ 1 2k1 k2
k= 2m E ; k = 2m(E − E 0 )
k2 − k12
B=i 2 sin k2 a eik1 a A .
with E 0 < 0 and obtain 2k1 k2
√ The reflection coefficient with cos2 x = 1 − sin2 x
E − E 0 /2 − E(E − E 0 ) 2 2
R= √ .
E − E 0 /2 + E(E − E 0 ) |B|2 k1 − k22 sin2 k2 a
R= = 2
|A|2 4k2 k2 + k2 − k2 sin2 k2 a
For E 0 = 0 ⇒ R = 0, for E 0 → −∞ ⇒ R = 1. 1 2 1 2
For E 0 = −E the kintetic energy of the particle and the transmission coefficient is:
becomes for x > 0 2E kin (x < 0). The reflection
|A |2 4k12 k22
coefficient is then T= = 2 .
√ |A| 2
4k12 k22 + k12 − k22 sin2 k2 a
3−2 2
R= √ = 0.029 . One can readily prove that R + T = 1. With
3+2 2
k12 = (2m E/2 ) and k22 = 2m(E − E 0 )/2 the
For E = − 12 E 0 we obtain: transmission becomes
√ 4E(E − E 0 )
2− 3 T= * √ +.
R= √ = 0.072 . 4E(E − E 0 ) + E 02 sin2 a 2m(E − E 0 )
2+ 3 (1)
This shows that with increasing step heights R Dividing the nominator and denominator by
increases. This is completely analogous to the re- (4E E 0 ) and using the relation sin(ix) = i sinh x we
flection of optical waves at a boundary between two obtain for E > E 0 the result (4.26a). For E > E 0
media with refractive indices n 1 and n 2 , where the transmission becomes T = 1 for
% % a
% n 1 − n 2 %2
% = ∆n
2
% 2m(E − E 0 ) = nπ
R=%
n1 + n2 % (2n)2 h 2a
⇒ λ= √ = , n = 1, 2, 3 .
with n = 12 (n 1 + n 2 ). 2m(E − E 0 ) n
Chapter 4 521
For a potential well with depth E 0 the potential

energy is E pot < 0 if we choose E pot = 0 outside
the well. In (4.26a) one has to change the sign
of E 0 . With the numerical data of Problem 4.2 (E =
0.4 eV, E 0 = −0.5 meV, a = 1 nm) we then obtain
from (4.26a)
1 + 0.8
T= √
1 + 0.8 + 0.31 sin2 a 2m × 0.9 meV/
1.8
= = 0.994 ,
1.8 + 0.31 sin2 (6.46)
where we have used sin ix = i sinh x.
5. For a potential well with infinitely high walls the
bound energy levels for a well with depth (−E 0 )
Fig. S.6.
are
2 π 2 2
En = n ≤ E0 .
2m a2 where the phase ϕ determines the amplitude of ψII
Inserting the numerical values a = 0.7 nm, E 0 = for x = 0 and x = a.
10 eV gives:
ψIII = A3 e−αx for x≥a.
2
−49 n −18
E n = 1.1 ×10 J ≤ 1.6 ×10 J. From the boundary conditions
m
ψIII (0) = ψII (0) ; ψII (a) = ψIII (a) (1)
a) Electrons with mass m = 9.1 ×10−31 kg:
we obtain:
E n = 1.2 ×10−19 n 2 J
A1 = A2 sin ϕ , (2)
1.6 ×10−18
⇒ n2 ≤ = 12.9 ⇒ n ≤ 3 . A3 = A2 sin(ka + ϕ) e−αa . (3)
1.2 ×10−19
There are only three bound levels in the well. From the continuity of the derivatives one obtains:
b) Protons with mass m = 1.67 ×10−27 kg: ψI (0) = ψII (0) ⇒ αA1 = k A2 cos ϕ .
⇒ E n = 5.59 ×10−23 J × n 2 This gives with (2):
⇒ n 2 ≤ 2.4 ×104 α = k cot ϕ ⇒ ϕ = arctan(k/α) . (4)
⇒ n ≤ 155 .
From the condition
% %
c) With the exact solution for the potential well d(ln ψII ) %% d(ln ψIII ) %%
=
with finite wall heights the wave functions are no dx %x =a dx %x =a
longer zero for x = 0 and x = a, but they penetrate one obtains:
a little bit into the wall regions (Fig. S.6). As was
discussed in Sects. 4.2.2 and 4.2.4 we now have the ϕ = −ka − arccot(k/α) + nπ . (5)
wave functions The comparison of (4) and (5) gives for k the
ψI = A1 eαx for x≤0 condition:
with ka = nπ − 2 arccot(k/α)
1 and the energy levels:
α= 2m(E 0 − E) ;
2 kn2 2
ψII = A2 sin(kx + ϕ) for 0 ≤ x ≤ a , En = = [nπ − 2 arccotg(k/α)]2 .
2m 2ma2
For E 0 = ∞ ⇒ α = ∞ and the arccotg becomes ∂ϑ zy/r 2

zero. This gives the results =
∂y x 2 + y2
2 π 2 2 y ∂ϕ x ∂ϕ
kn = nπ/a ⇒ E n = n , ϕ = arctan ⇒ = 2 , = 0.
2ma2 x ∂y x + y2 ∂z
which was derived from the well with infinitely Inserting these relations into (1) gives:
high walls.
#
6. At the lowest energy (zero-point energy) the par- ∂ y ∂
ticle is restricted to the interval ∆x = x2 − x1 L̂ x = −i 0 −
∂r x +y
2 2 ∂ϑ
between two points $
zx ∂
x1,2 = ±(2E pot /D)1/2 , − 2
x + y2 ∂ϕ
# $
which are the intersections of the energy level ∂ ∂
= +i sin ϕ + cot ϑ cos ϕ .
1 ∂ϑ ∂ϕ
E(v = 0) = D/m .
2 The components L̂ y and L̂ z can be obtained in an
With the parabolic potential analogous way. In order to obtain L̂ 2 we use the
1 2 relation:
E pot = Dx
2
L̂ 2 = L̂ 2x + L̂ 2y + L̂ 2z
we obtain:
8 1/2
and we have to calculate L̂ 2x , L̂ 2y and L̂ 2z :
∆x = 2 D/m D
8√ 1/2
∂ ∂
=2 D·m . L̂ x = − sin ϕ + cot ϑ cos ϕ
2 2
∂ϑ ∂ϕ

7. The x-component of L̂ is ∂ ∂
× sin ϕ + cot ϑ cos ϕ .
∂ϑ ∂ϕ
∂ ∂
L̂ x = −i y − z
∂z ∂y The differential operators ∂/∂ϑ and ∂/∂ϕ act on all
∂ ∂r ∂ ∂ϑ ∂ ∂ϕ ∂ functions, after multiplication of the two brackets,
= + + stand behind these operators,
∂z ∂z ∂r ∂z ∂ϑ ∂z ∂ϕ
# This yields the four terms:
∂r ∂r ∂
⇒ L̂ x = −i y − z
∂z ∂y ∂r ∂ ∂ ∂2
sin ϕ sin ϕ = sin2 ϕ 2 ;
∂ϑ ∂ϑ ∂ ∂ϑ ∂ϑ
+ y −z ∂ϑ
∂z ∂y ∂ϑ ∂ ∂
$ sin ϕ cot ϑ cos ϕ
∂ϕ ∂ϕ ∂ ∂ϑ ∂ϕ
+ y −z . (1)
∂z ∂y ∂ϕ 1 ∂ ∂ ∂
= sin ϕ cos ϕ − 2 + cot ϑ ;
sin ϑ ∂ϕ ∂ϑ ∂ϕ
with
∂ ∂
r = x 2 + y2 + z 2 cot ϑ cos ϕ sin ϕ
∂ϕ ∂ϑ
∂r z ∂r y
⇒ = , = . ∂ ∂ ∂
∂z r ∂y r = cot ϑ cos ϕ + cos ϕ sin ϕ
2
;
/ 0 ∂ϑ ∂ϑ ∂ϕ

z ∂ ∂
ϑ = arccos cot ϑ cos ϕ cot ϑ cos ϕ
x 2 + y2 + z 2 ∂ϕ ∂ϕ

∂ϑ z /r − 1
2 2 ∂ ∂2
⇒ = = cot ϑ − cos ϕ sin ϕ + cos ϕ 2 .
2 2
∂z x 2 + y2 ∂ϕ ∂ϕ
Chapter 5 523
Similar terms are obtained for L̂ 2y and L̂ 2z . The is the de Broglie wavelength of the particle within
addition finally gives (4.111) when the relation the range of the barrier.
b) E = 0.8 eV, E 0 = 1 eV ⇒ E/E 0 = 0.8, m =
∂ ∂2 1 ∂ ∂ 9.1 ×10−31 kg.
cot ϑ + = sin ϑ
∂ϑ ∂ϑ 2 sin ϑ ∂ϑ ∂ϑ
α = 2m(E − E 0 )/
is used.
8. The wave function within the range x < 0 and x > a 2 × 9.1 ×10−31 (0.2 × 1.6 ×10−19 ) −1
= m
is for a penetration depth δx 1.06 ×10−34
√ = 2.28 ×109 m−1
ψ (δ x) = C e(i/ ) 2m(E0 −E)δ x .
a = 10−9 m ⇒ sinh2 (αa) = 24.4
The probability of finding a particle in this range is −0.2
proportional to |ψ(δ x)|2 . It decreases to 1/ e for ⇒ T= ≈ 0.03 .
0.2 − 0.28 × 24.4

δx = √ . For E = 1.2 eV
2m(E 0 − E) −0.2
⇒ T= = 0.625 .
Example: m = 9.1 ×10−31 kg (electron mass), E = −0.2 − 0.208 sinh2 2.28
−19
2 E 0 , E 0 = 1 eV = 1.6 ×10
1
J 10. The energy levels in the two-dimensional quadratic
1.06 ×10−34 potential well are, according to (4.66):
⇒ δx = √ m
1.82 ×10−30 × 0.8 ×10−19 2 π 2 2
E nx , n y = n x + n 2y ≤ E max . (2)
= 0.28 nm . 2ma 2
9. For E = 12 E 0 we obtain from (4.26a): Inserting the numerical values

0.5 m = 9.1 ×10−31 kg ,
T=
0.5 + 0.5 sinh2 2π a = 10−8 m ,
= 1.4 ×10−5 . E max = 1 eV
With the approximation (4.26b) we obtain for E = gives the conditions
0.5 E 0 : 2
n x + n 2y ≤ 2.66 ×102
T = 4 e−4π = 1.395 ×10−5 ,
⇒ n x , n y ≤ 16 and n 2x + n 2y ≤ 266 .
which is practical identically to the value of the
correct calculation. All possible levels can be visualized as points in
For E = 13 E 0 : a two-dimensional space with the axis n x and n y .
They fill a quarter of a circular area (π/4)(n 2x + n 2y )
2/3 because n x , n y ≥ 0. There are therefore approxi-
T= √
2/3 + 3/4 sinh2 2π 2 mately (π/4) × 266 = 208 energy levels that obey
these conditions. Some of them are degenerate.
= 5.1 ×10−8 . These are levels with the same value of n 2x + n 2y .
Maximum transmission T = 1 is reached for E > Examples are: n x = n y = 5 and n x = 1, n y = 7 and
E 0 if sin2 (iaα) = 0 n x = 7, n y = 1.
n
⇒ a 2m(E − E 0 ) = nπ = h
2
n Chapter 5
⇒ a = λ,
2
where 1. The expectation value of r is defined as

h
λ= √ r = ψ ∗rψ dτ
2m(E − E 0 )
with dτ = r 2 sin ϑ dr dϑ dϕ. In the 1s state of the where IP = 13.6 eV is the ionization potential.
H atom Therefore all lines appear in the emission that start
from levels n ≤ 6. These are for n = 6
1
ψ = √ 3/2 e−r/a0
πa0 6s → 5 p , 4 p , 3 p , 2 p ,
∞ 6 p → 5s , 4s , 3s , 2s , 1s ,
1
⇒ r = 3 4π e−2r/a0 r 3 dr 6d → 5 p , 4 p , 3 p , 2 p ,
πa0
0 6 f → 5d , 4d , 3d ,
4 3! 3
= 3 = a0 . 6g → 5 f , 4 f ,
a0 (2/a0 )4 2
and similar expressions for n = 5, 4, 3, 2.
The expectation value of r is therefore larger than
Since all terms with equal quantum number j =
the Bohr radius a0 ! The expectation value of 1/r is
l + s are degenerate, many of these lines are
1 2 ∞ coincident in energy and are not separated.
1 1 3. a) For the ground state 1s of the H atom r = a0
= 3 4π e−2r/a0 r dr
r πa0 according to Bohr’s model. (Note, however, that
0
r = 32 a0 , see Problem 5.1.)
4 a02 1
= = . The excitation energy of 12.09 eV reaches levels
a03 4 a0 with energies
For the 2s state the wave function is Ry∗
E n = IP − = 12.09 eV
1 r n2
ψ(2s) = √ 3/2
2− e−r/2a0 13.599
4 2πa0 a0 ⇒ n2 = = 9 ⇒ n = 3.
∞ 13.599 − 12.09
4π r 2 −r/a0 3
⇒ r = 2 − e r dr Since r ∝ n 2 the Bohr radius becomes r(n = 3) =
16 × 2πa03 a0 9a0 .
0
∞ # b) For the excitation energy E e = 13.387 eV we
1 4r 4 −r/a0 obtain in a similar way
= 3 4r 3 e−r/a0 − e
8a0 a0
0 13.599
$ n2 = = 64 ⇒ n = 8 .
r5 0.212
+ 2 e−r/a0 dr
a0 r(n = 8) = 64a0 .
1 * + 4. In the classical model,
= 3 24a04 − 96a04 + 120a04 = 6a0 .
8a0 µe e
µe = −e/(2m e )l ⇒ =−
A similar calculation for 1/r yields l 2m e
1 2 is constant and independent of the principal
1 1
= . quantum number n.
r 4a0 In the quantum-mechanical description the expec-
2. The excitation energy of E e = 13.3 eV can populate tation values:
the upper levels E n with energies e
µz = −m l , −l ≤ m l ≤ +l ,
∗ 2m e
Ry
E n = IP − ≤ Ee 2 e2 2
n2 µe = l(l + 1) 2 .
∗
Ry 13.6 4m e
⇒ n2 ≤ = = 45.3
IP − E a 13.6 − 13.3 Although the number of possible components µz
⇒ n ≤ 6, depend on l, the values are still independent of n.
Chapter 5 525
5. a) The velocity of the electron on the lowest Bohr and shows that the model of a charged sphere for
orbit is v1 = c/137. Its relative mass is then the electron is not correct. The definition of the
electron spin as the angular momentum of a sphere
m0 1 v2
m(v) = ≈ m0 1 + 2 with mass m e is wrong!
1 − v2 /c2 2c b) The rotational energy is:
−5

= m 0 1 + 2.66 ×10 . 1 2 1 1
E rot =Iω = m er 2 ω2 = m e veq 2
.
The mass increase ∆m 1 = m − m 0 = 2.66 × 2 5 5
10−5 m 0 . For n = 2, because of v ∝ 1/n, v(2s) = For r = 1.4 ×10−15 m ⇒ E rot = 6 ×10−9 J, while
3.65 ×10−3 c the mass energy E 0 = m e c2 = 8 ×10−14 J is much
smaller. This shows again that the mechanical
⇒ m(v) = m 0 1 + 6.6 ×10−6
model of the electron can not be correct.
⇒ ∆m 2 = 6.6 ×10−6 m 0 . 7. The Zeeman splitting of the 22 S1/2 -state is,
The difference is: according to (5.7),
δm = ∆m 1 − ∆m 2 ∆E s = gj µB B ,
= 2.0 ×10−5 m 0 = 1.8 ×10−35 kg . with gj = gs ≈ 2. For the 32 P1/2 state it is (see
Fig. S.7):
b) The energy difference is:
∆E p = gj µB B
∆E = E(2s) − E(1s) = 10 eV = 1.6 ×10−18 J .
with
The potential energy E pot = −2E kin . Since 1 3
+ 12 2 −1×2
3
2
1 gj = 1 + 2 2
= .
E = E pot + E kin = E pot ⇒ E pot = 2 · E . 2 1 3
2 2
3
2
The difference in potential energy corresponds to The four Zeeman lines (Fig. S.7) appear as two
a mass difference pairs, where the smaller distance is
2
∆m = m 1 − m 2 = 2∆E/c2 ∆ν1 = µB B/h
3
= −3.6 ×10−35 kg .
and the larger distance is
Both effects are opposite in sign. Because the rela- 4
tive velocity effect m v (1s) > m v (2s) is only 1/2 of ∆ν2 = µB B/h .
3
the potential energy effect, the mass of the atom is
larger in the 2s state than in the 1s state.
6. a) The angular momentum of a spherical body,
rotating around an axis through its mass center is
2
|s| = Iω = m er 2 ω = 3/4 .
5
The velocity at the equator is
5√
vequator = rω = 0.75/(m er) .
2
For r = 1.4 ×10−15 m, m e = 9.1 ×10−31 kg we
obtain
v = 1.8 ×1011 m/s c !
For r = 10−18 m ⇒ v = 2.5 ×1014 m/s. This is
a contradiction to the special theory of relativity Fig. S.7.
For B = 1 Tesla, µB = 9.27 ×10−24 J/T we obtain corresponding to the transition between the HFS
components has a frequency
∆ν1 = 9.3 ×109 s−1 , ∆E c
∆ν2 = 1.86 ×1010 s−1 . ν= =
h λ
a) In order to resolve these components with with ∆E = 9.46 ×10−25 J. With µK = 5.05 ×
a central frequency ν = 4.5 ×1014 s−1 the spectral 10−27 J/T the magnetic field is
resolving power has to be ∆E 9.46 ×10−25
B= = T
% ν % %% λ %% 4.5 ×1014 5.58µK 5.58 × 5.05 ×10−27
% % % %=
% %=% = 4.8 ×104 . = 33.5 T .
∆ν ∆λ % 9.3 ×109
The resolving power of a grating spectrograph is The magnetic field produced by the electron in the
% % 1s state of hydrogen at the location of the pro-
% λ % ton is therefore with 33.5 T much larger than fields
% %
% ∆λ % ≤ m N , obtained in the lab.
9. The frequencies of the transitions are given by
where m is the interference order and N the number
of illuminated grooves. For m = 2 we then obtain: ∗ 1 1 3
hν = Ry − = Ry∗ .
1 4 4
4.8 ×104
N≥ = 24,000 . The Rydberg constant
2
e4 mnme
b) The Fabry–Perot interferometer with mirror Ry∗ = µ with µ =
separation d = 1 cm has a free spectral range
2 2
8ε0 h mn + me
depends on the mass m n of the nucleus. For the
c 3 ×108 −1
δν = = s = 1.5 ×1010 s−1 . H atom
2d 2 ×10−2 1
µ = me = m e · 0.999456 .
With a finesse 1 + 1836
1
√
∗ π R For the D = 21 H isotope
F =
1− R 1
µ = me = m e · 0.999728 .
the minimum separation of two resolvable lines is: 1 + 3672
1
∆ν = δν/F ∗ . For the isotope T = 31 H it is
With R = 0.95 ⇒ F ∗ = 61 and µ = m e · 0.999818 .
1.5 ×1010 The wavenumber and frequency of the Lyman α-

∆ν = ≈ 2.5 ×108 s−1 . lines are then:
61
In order to resolve all four Zeeman lines, the ν 11 H = 82,258.2 cm−1
magnetic field has to be at least B ≥ 0.026 T. ⇒ ν = 2.466039 ×1015 s−1 ,

8. The potential energy of a magnetic dipole in ν 21 D = 1.00027ν 11 H = 82,280.6 cm−1 .
a magnetic field is:
The difference is
E = −µ · B .
∆ν1 = ν 21 D − ν 11 H
The magnetic moment of the proton is = 22.4 cm−1
3
µp = 2.79µK . ν 1 T = 1.00036ν 11 H = 82,288.0 cm−1

∆ν2 = ν 31 T − ν 11 H
The separation of the two hyperfine components
is ∆E = 5.58µK · B. The line with λ = 21 cm, = 29.8 cm−1 .
Chapter 6 527
The hyperfine-splittings are: dτ = r12 dr1 sin ϑ dϑ dϕ

a) 11 H: E HFS = ±µ · B ⇒ ∆E = 2|µ| · |B|
Z 3/2
with B = 35 T (see Problem 5.8) and µ = ψ1 s = √ 3/2 e−Zr1 /a0 .
2.79µK ⇒ ∆E = 5.58 µK · B = 9.43 ×10−25 J = ˆ πa0
5.9 ×10−6 eV. Inserting these relations with Z = 2, into the
b) 21 D: The internal magnetic field is caused by integrand we obtain for the integral
the electron and therefore the same for all three
isotopes. The two hyperfine components have the |ψ1 s |2 2
I= r1 sin ϑ dr1 dϑ dϕ
energy r⎡
12
A r2 −Z2r1 /a0 2 r
2 +r1
E HFS = · [F(F + 1) − J(J + 1) − I(I + 1)] . Z 3π ⎢ e r1
2 = ⎣ dr1 dr12
πa03 r1 r2
r1 =0 r12 =r2 −r1
With F = 3/2, J = 1/2 we obtain ⎤
∞ r
1 +r2
e−Z2r1 /a0 r1
A + dr1 dr12 ⎦ .
E HFS = . r2
2 r1 =r2 r12 =r1 −r2
With F = 1/2 ⇒ FHFS = −A. The splitting is then: (2)
∆F = 32 A with
For ϑ = 0 we have:
A = gI µK · B J / J(J + 1) ⎧
√ ⎨r − r for r < r ,
2 1 1 2
= 2gI µK B J / 3 . r12 =
⎩r − r for r > r .
1 2 1 2
c) 31 T: Here is I = 3/2; ⇒ F = 2 and F = 1
3 5 For ϑ = 0 ⇒ r12 = r1 + r2 . The integration of the
E(F = 2) = + A ; E(F = 1) = − A first term in (2) gives
4 √ 4

⇒ ∆E = 2A = 4gI µK B J / 3 . r2 a0 a02 a3
I1 = − − 2 − 0 3 e−2Zr2 /a0
Z Z 2r2 Z
a03
+
Chapter 6 2r2 Z 3
and for the second term:
1. The potential experienced by the second electron
a0r2 a2
in the He atom is (see Fig. S.8) I2 = + 02 e−2Zr2 /a0 .
Z 2Z
Ze e |ψ1 s (r1 )|2
φ(r2 ) = − + dτ , This gives, with r = r2 , the total potential felt by
4πε0r2 4πε0 r12
the second electron:
(1)
(Z − 1)e e Z 1
2
r12 = r12 + r22 − 2r1r2 cos ϑ φ(r) = − − + e−2Zr/a0
4πε0r 4πε0 a0 r
⇒ r12 dr12 = r1r2 sin ϑ dϑ
with Z = 2 for the He atom.

2. The charge density of the two 1s-electrons is
approximately
2e −2R/b
η = −2e · ψ 2 (1s) = − e
b3 · π
Fig. S.8. with b = a0 /Z eff .
⎡ r
0
4e ⎣ 2R2 −2R/b
=− 3 e dR
b r0
R=0
⎤
∞
⎥
+ 2R · e−2R/b dR⎦ .
R=r0
The integral can be solved analytically

η 2e r0
dτ = − 1 + e−2r0 /b 1 + .
r r0 b
Fig. S.9.
The potential then becomes with b = a0 /Z eff and
when we rename r0 → r:
# $
The potential, experienced by the 2s electrons in e −2Z eff ·r/a0 rZ eff
φ(r) = 1+2e 1+ .
the field of the nucleus and the two 1s-electrons is 4πε0r a0
(Fig. S.9):

3e 1 η
φ=+ − dτ . 3. The mean distance between the atoms is d = n −1/3 .
4πε0r0 4πε0 r The de Broglie-wavelength λdB becomes larger
The integral can be solved as follows: than d for

η h h
dτ >d ⇒ v< .
r mv mn −1/3
∞ π 2π −2R/b
2e e The mean velocity is
=− 3 R2 sin ϑ dR dϑ dϕ
b π r 8kT
R=0 ϑ=0 ϕ=0
v= .
∞ π πm
2e R2 e−2R/b sin ϑ dR dϑ
=− 2π . This gives the condition for the temperature T :
b3 π R2 + r02 − 2Rr0 cos ϑ
R=0 ϑ=0 πh 2 n 2/3
T< .
With r 2 = R2 + r02 − 2r0 R cos ϑ ⇒ r dr = r0 R · 8k · m
sin ϑ dϑ the integral then becomes:
Example: n = 1012 /cm3 = 1018 /m3 and m =
∞ 23 AMU = 23 × 1.66 ×10−27 kg
η 4e R −2R/b
dτ = − 3 e dR dr .
r b r0
R=0 r
⇒ T < 3.3 ×10−7 K = 330 nK .
Is the point A (location of 2s-electron) outside the Below this temperature the particles are no lon-
charge distribution of the 1s-electrons (r0 > R) the ger distinguishable because their location can only
integration over r extends from r0 − R to r0 + R. be defined within a volume λ3dB . The atoms form
For r0 < R (2s-electron inside the core) it extends a Bose–Einstein condensate of identical particles.
from R − r0 to R + r0 . This gives: 4. The potential energy of the two electrons is
⎡
r0 r 0 +R (Fig. S.10)
η 4e ⎢ R −2R/b
dV = − 3 ⎣ e dR dr 4e2 e2
r b r0 E pot = − +
R=0 r=r0 −R 4πε0r1 4πε0 (2r1 )
⎤
∞ 0
R+r 7 e2 7 e2
R −2R/b ⎥ =− =− ,
+ e dR dr ⎦ 8 πε0r1 4 πε0 a0
r0 with r1 = a0 /2 .
R=r0 r=R−r0
Chapter 6 529
#
Fig. S.10. 1 1 Z
× + + e−2Zr/a0
r r a0
!
r 2 −r/a0
× 2− e dτ
a0
∞ #
4 4 r
= − + e−r/a0
r a0 a02
r=0
The kinetic energy of the two electrons is:
4 4(Z − 1) (4Z − 1)r Zr 2
+ + − + 3
2m e v2 r a0 a02 a0
E kin = = m e v2 .
2 $ π 2π
−(2Z+1) r/a0
With ×e 2
r dr sin ϑ dϑ dϕ
Zh h ϑ=0 0
v= =
2πma0 πma0 ∞ #
4r 2 r 3
we obtain: = 4π 4r − + 2 e−r/a0
a0 a0
r=0
h2 $
E kin = . 4r 2 7r 3 2r 4
π 2 ma02 + 4r + − 2 + 3 e−5r/a0 dr
a0 a0 a0
The total energy of the system is then: #
4 8 2
= 4π 4a02 − 8a02 + 6a02 + a02 + a
7 e2 h2 25 125 0
E=− + 2 2. $
4 πε0 a0 π ma0 42 2 48 2
− a0 + a0
Inserting the numerical values yields 625 3125
E = −1.30 ×10−17 J = −82 eV . 6788 2

= 4π a
The experimental result is E = −78.9 eV. This 3125 0
e2
shows that our simple model approaches the real ⇒ E pot (2s) = − 0.272
situation quite well. The small difference comes 4πε0 a0
partly from the fact that we have neglected the = −7.39 eV .
relativistic mass increase. A similar calculation for the 3s state gives:
5. The expectation value of the potential energy e ·
φ(r) of an electron in the 2s state is E pot (3s) = −3.19 eV

⇒ ∆E pot = 4.2 eV
E pot = e ψ2∗ φ(r)ψ2 dτ2 .
because E kin ≈ − 12 E pot we obtain
Assuming a spherically symmetric wave func-
tion ψ2 (2s) as in the H atom (because the electron ∆E = ∆E pot + ∆E kin
moves in a potential that is essentially a Coulomb 1
≈ ∆E pot ≈ 2.1 eV .
potential with the effective charge Z eff = 1) we can 2
write: This agrees fairly well with the experimental value
∆E exp = 2.3 eV, obtained from the difference of
1 r 2 −r/a0
|ψ2 | 2 = 2 − e the wavenumbers ν(3s ↔ 1s) − ν(2s ↔ 1s) of the
32πa03 a0
two-photon allowed transition.
e2 6. The largest mean distance between the electrons
⇒ E pot = −
4πε0 × 32πa03 is realized if the total spin of all electrons has its
µ
maximum allowed value. Since for this case the The radius rn of the myon is
spin function is symmetric, the spatial part of the
n 2 a0
wave function is antisymmetric with respect to ex- rnµ = .
changing two electrons. This means that the wave Z 206.6
function ψ(r1 , r2 ) has nodes for r1 = r2 . There- The smallest radius of the electron is r1el = a0 /Z.
µ
fore the potential energy of the mutual repulsion The condition r1el = rn gives:
is minimized, which gives a minimum for the total
n2
energy. = 1 ⇒ n ≈ 14 .
7. With the screening constant S, the potential energy 206.6
µ
of a Rydberg electron can be written as The radius r14 of the myon is about the same as the
lowest radius r1el of the electron orbit.
(Z − S)e2
E pot = − . 9. The potential energy of the electron with the wave
4πε0r function ψ(r) is (see Problem 6.1)
For the total energy (note that E kin = − 21 E pot ) we
obtain E pot = +e |ψ(r)| 2 φ(r) dr .
(Z − S)e2 For the 3s electron the probability to find the elec-
E=−
8πε0r tron inside the n = 2 shell is larger than for the
= E kin + E pot . 3 p electron, because the 3 p-functions has a node at
r = 0. Therefore the shielding of the nuclear charge
According to the Rydberg formula (6.32) the
is smaller for the 3s electron than for the 3 p elec-
energy can be also expressed by
tron. The potential energy is lower and therefore its
−(Z − S)2 Ry∗ Ry∗ total energy.
E=− = − .
n2 (n − δ)2 10. The potential energy of the second electron in the
The comparison yields the relation H− ion is
n E pot (r2 ) = +eφ(r) ,
S= Z−
n −δ
where the potential φ(r) has been calculated in
between the screening constant S and the quantum Problem 6.1 and where we have to insert Z = 1.
defect δ. For δ → 0 we obtain S = Z − 1, which
e 1 1
means a Coulomb potential with Z eff = Z − S = 1. ⇒ φ(r) = − + e−2r/a0 .
8. For the myonic atom the reduced mass is 4πε0 a0 r
mµ · mN The wave functions of the second electron can be
µ= . approximated by the hydrogen wave function
mµ + mN
With m µ = 206.76 m e , m N = 140 × 1836 m e we 1
ψ(r) = √ 3/2 e−r/a0
obtain µ = 206.6 m e . πa0
⇒ Ryµ∗ = 206.6 · Ry∗∞ when we neglect the repulsion between the two
∗∞ 2 electrons. The potential energy is then
206.6Ry Z
⇒ En = −
n2 min
E pot = +e |ψ(1s)| 2 φ(r) dτ
The energy of the photon on a tansition n = 2 →
n = 1 is ∞
4πe2 1 1
=− + e−4r/a0 r 2 dr
∗∞ 2 1 1 4πε0 πa03 a0 r
hν = 206.6Ry Z − 0
1 4
3 e2 3 2 3 e2
= 602 × 206.6 × 13.6 eV =− a0 = −
4 πε0 a03 32 8 4πε0 a0
= 7.59 ×106 eV = 7.59 MeV . = −10.2 eV .
Chapter 7 531
The crude approximation gives a binding energy which form closed shells is spherically symme-
tric. The valence electron moves in a spherical
E B = E pot + E kin = −5.1 eV potential, which is nearly a Coulomb potential
of the second electron. It is higher than the ex- (∼ 1/r) for larger r, but deviates from it for
perimental value of −2.5 eV, because we have small r.
neglected the repulsion between the two electrons. 13. The potential energy of the electron is
11. The energy of the state with principal quantum
e2
number n is E pot (x) = − − eE 0 x
2
4πε0r
Z eff n2 En with x = r cos α .
E n = −Ry∗ ⇒ Z 2
= − ; En < 0 .
n2 eff
Ry∗
With Ry∗ = 13.6 eV one obtains: In the x-direction α = 0 ⇒ cos α = 1. We than can
write:
4 × 5.39
2
Z eff (n = 2) = = 1.58 dE pot e2
13.6 = − eE 0 .
⇒ Z eff = 1.26 . dr 4πε0r 2
The nuclear charge Ze with Z = 3 is screened by The maximum of the potential barrier is at
the two 1s electrons by 1.74e. dE pot / dr = 0
For the Rydberg level with n = 20 we obtain: 1/2
e
400 × 0.034 ⇒ rm =
2
Z eff (n = 20) = ≈1 4πε0 E 0
13.6
⇒ Z eff = 1 . e3 E 0
⇒ E pot (rm ) = − .
πε0
For high Rydberg levels the screening of the
nuclear charge Ze is nearly complete by the (Z − 1) Without the external field E pot (r) ⇒ 0 for
electrons of the atomic core. r → ∞. The lowering of the ionization potential
12. For all alkali atoms there is a single electron in the is, therefore,
valence shell with principal quantum number n = 2
(Li), n = 3 (Na), n = 4 (K), n = 5 (Rb), n = 6 (Cs). e3 E 0
∆(IP) = − .
The larger the n is, the better the shielding of the πε0
nuclear charge Ze by the Z − 1 electrons in the core.
This implies that Z eff decreases with increasing n Due to the tunnel effect, the effective decrease of
and the binding energy of the valence electron (this IP is even slightly larger.
is the ionization energy of the atom) decreases with
increasing n.
The experimental technique for the determina- Chapter 7
tion of the binding energy is, for instance, the
photoionization of the atom. 1. a) The total emitted energy is

A(E n ) + hν → A+ + e− (E kin ) . WFl = N 32 P3/2 hν = 108 × 3.4 ×10−19 J
One can measure the frequency νg , where = 3.4 ×10−11 J .
E kin (e− ) = 0 ⇒ −E n = hν . The time dependent fluorescence power can be

calculated as
The approximate calculation of the binding
energy is based on the Hartree method (see PFl = P0 e−t/τ ,
Sect. 6.4.2), which converges rapidly because
the charge distribution of the core electrons, where excitation at t = 0 is assumed.
The emitted energy is related to the power by

∞ ∞
WFl = PFl dt = P0 e−t/τ dt = τ · P0
0 0
⇒ P0 = 3.4 ×10−11 J/1.6 ×10−8 s
= 2.1 ×10−3 W .
Fig. S.11.
b) The angular distribution is
W(ϑ) = W0 sin2 ϑ ,
2π
+π/2 b) The collimation ratio of the atomic beam is
Wtotal = W0 sin ϑ dϑ dϕ
2 (Fig. S.11)
ϕ=0 ϑ=−π/2 b 1
# $+π/2 ε= = .
1 1 2d 200
= 2πW0 ϑ − sin 2ϑ Since the nozzle diameter is small compared to b
2 4 −π/2
we can regard the nozzle as a point-like source of
= π W02
atoms. The transverse velocity distribution f(vx ) is
⇒ W0 = Wtotal /π 2 . determined by |vx | < v sin ε. The reduced Doppler
Within the angular range ∆ϑ = 0.1 Sterad around width is then:
ϑ = 90◦ the energy (δνD )beam = δνD (v) sin ε .
W(ϑ = π/2 ± ∆ϑ/2, ϕ = 0 ± ∆ϕ/2) With sin ε = 5 ×10−3 and δνD = 3.06 ×1010 s−1 we

π/2+∆ϑ/2
obtain:
= ∆ϕW0 × sin2 ϑ dϑ
(δνD )beam = 1.5 ×108 s−1 = 150 MHz .
ϑ=π/2−∆ϑ/2
c) The natural line width is
1 1
= W0 · ∆ϕ ∆ϑ + sin ∆ϑ
2 2 1 109 −1
δνn = = s = 132 MHz .
is emitted. For ∆ϑ 1 we have: 2πτ 2π 1.2
W = W0 · ∆ϕ∆ϑ . The measured line width is

The solid angle ∆Ω is δνexp ≈ (δν)2beam + (δνn )2 ≈ 200 MHz .
∆Ω = ∆ϑ ∆ϕ = 0.1 Sterad The hyperfine splitting is
0.1
⇒ W = 0.1 W0 = 2 Wtotal ≈ 0.01 Wtotal . δνHFS (1s) = 1.4 ×109 s−1 .
π
This means that 1% of the total energy is emitted It can therefore be readily resolved.
in a direction perpendicular to the dipole axis into 3. The natural line width of the Ca transition is
the solid angle ∆Ω = 0.1 Sterad.
1 104 −1
2. a) The Doppler width is δνn = = s = 410 Hz
2πτ 2π 3.9
δνD = 7.16 ×10−7 ν0 T/M mol/(g K) . The interaction time ∆T should be longer than:
With T = 300 K, M = 1 g/mol, ν0 = 2.47 × 1 1s
1015 s−1 we obtain ∆T ≥ = = 53 µs
2π∆ν 2π 3 ×103
δνD = 3.06 ×1010 s−1 = 30.6 GHz in order to reach a line width of ∆ν = 3 kHz. The
c natural line width is negligible compared with the
⇒ |∆λD | = 2 δνD = 1.5 ×10−3 nm .
ν transit time broadening.
Chapter 7 533
The mean velocity of the Ca atoms is at an oven we obtain with δνD = 6.77 ×109 s−1 for ν1 − ν0 =
temperature T = 900 K 0.1 δνD :

8kT 8 × 1.38 ×10−23 × 9 ×102 m α(ν1 ) = α(ν0 ) e−0.028 ln 2
v= =
πm π × 40 × 1.66 ×10−27 s = 0.98 α(ν0 ) .
= 690 m/s . For a Lorentzian profile with δνn = 1.14 ×108 s−1
The minimum interaction zone is then we have:
∆s = v ∆T = 6.9 ×102 × 5.3 ×10−5 m ν1 − ν0 = 0.1 δνD = 6.77 ×108 s−1

2
= 3.7 ×10−2 m = 37 mm . 5.7 ×107
⇒ α(ν1 ) = α(ν0 ) 2 2
4. a) The wavelength λ of a transition between energy 6.77 ×108 + 5.7 ×107
levels with term values Ti , Tk is = 7 ×10−3 α(ν0 ) .
1 1
λik = = cm = 501.7 nm . For ν1 − ν0 = δνD we obtain for the Gaussian
Ti − Tk 19,932 profile:
b) The natural line width is:
α(ν1 ) = 0.146 α(ν0 )
1 1 109 103
δνn ≤ + = + and for the Lorentzian profile:
2πτi 2πτk 2π 1.4 2π
= 1.14 ×108 s−1 = 114 MHz . α(ν1 ) = 7 ×10−5 α(ν0 ) .
c) The Doppler width is For ν1 − ν0 = 10 δνD
−7

δνD = 7.16 ×10 ν0 T/M[mol/(g K)] ⇒ α(ν1 ) = α(ν0 ) e−278 = 2 ×10−120 α(ν0 )
c 3 ×108
ν0 = = s−1 for the Gaussian profile and
λ 5.017 ×10−7 2
= 5.98 ×1014 s−1 5.7 ×107
α(ν1 ) = α(ν0 ) 2
T = 103 K , M = 4 g/mol 6.77 ×1010
9 −1
⇒ δνD = 6.77 ×10 s = 6.77 GHz . = 7 ×10−7 α(ν0 ) .
5. a) The Lorentzian line profile with half-width δνn for the Lorentzian profile.
is: Here the absorption by the Gaussian profile is negli-
(δνn /2)2 gible compared to the absorption by the Lorentzian
α(ν) = α(ν0 ) . profile.
(ν − ν0 )2 + (δνn /2)2
b) The relative absorption at ν = ν1 of the two
A wavelength difference ∆λ = 0.1 nm corresponds profiles becomes equal for:
to a frequency difference
(δνn /2)2 2
c
∆ν = (ν1 − ν0 ) = 2 ∆λ = 1.2 ×1011 s−1 = e− [(ν1 −ν0 )/0.6 δνD ]
λ (ν1 − ν0 ) + (δνn /2)
2 2
2 * +
0.57 ×108 ⇒ ln (δνn /2)2 + (ν1 − ν0 )2 − ln (δνn /2)2
⇒ α(ν1 ) = α(ν0 ) 2 2 = [(ν1 − ν0 )/0.6 δνD ]2 .
1.2 ×1011 + 0.57 ×108
= 2.25 ×10−7 α(ν0 ) . The numerical solution (which can be obtained with
the program “Mathematica”) depends on the ratio
For a Doppler-broadened absorption profile x = δνn /δν0 . For x = 0.01 ⇒ ν1 − ν0 = 439.6 δνn .

− (ν1 −ν0 )2 /(2δ νD )2 ln 2 For x = 0.1 ⇒ ν1 − ν0 = 27.8 δνn . For x = 1 ⇒
α(ν) = α(ν0 ) e ν1 − ν0 = 0.895 δνn .
6. The frequency of the K α lines of silver can be The natural line width of the Lyman α-line is
estimated for an effective charge Z eff = Z − 1 with 1
Z = 47 from the relation: δνn = = 7.4 ×107 s−1
2πτ(2 p)
1 1
hν = Ry∗ (Z − 1)2 − . since τ(2 p) = 2.1 ns.
n 21 n 22
The recoil shift is therefore only ∆νrecoil =
For n 1 = 1, n 2 = 2 and Ry∗ = 13.6 eV we obtain: 0.35 δνn . The Doppler width at T = 300 K is:
3 δνD = 3.06 ×1010 s−1 ⇒ ∆νrecoil δνD .
hν = 13.6 × 462 × eV = 21.6 keV
4
= 3.45 ×10−15 J 8. The effective lifetime is determined by
18 −1 1 1
⇒ ν = 5.22 ×10 s = + nσvr ,
c τeff τn
λ = = 5.75 ×10−11 m = 0.575 Å .
ν where vr is the mean relative velocity. From the re-
The experimental value is hν = 21.9 keV, λ = lation p = nkT we obtain for p = 1 mbar = 102 Pa
0.562 Å. The ionization energy of molybdenum is p 102 Pa
(see, e.g., the American Handbook of Physics) n= = m−3 .
kT 1.38 ×10−23 × 500
IP 42 Mo = 20.0 keV . ⇒ n = 1.45 ×1022 m−3

The kinetic energy of the photoelectron is then 8kT
vr =
E kin = hν − IP = (21.9 − 20.0) keV = 1.9 keV . πm
with
The velocity is m1m2
m= = 0.55m(Na) = 2.1 ×10−26 kg
v = 2E kin /m e = 2.6 ×107 m/s = 8.6 ×10−2 c . m1 + m2

7. The recoil momentum is 8 × 1.38 ×10−23 × 500 m
⇒ vr = = 915 m/s .
2π 2.1 π × 10−26 s
p = k with |k| = .
λ This gives
The recoil energy is 9
1 10
p2 2 k2 (hν)2
2
1 E phot = + 1.45 ×10 × 4 ×10 × 961 s−1
22 −19
E kin = = = = . τeff 16
2m 2m 2mc2 2 mc2 = 6.81 ×107 s−1
For the transition n = 2 → n = 1 in the H atom is ⇒ τeff = 14.7 ns .
hν = 10.2 eV and mc2 (proton) = 938.8 MeV
1 10.22 16 =
The effective lifetime is smaller by a factor 14.7
⇒ E kin = eV = 5.5 ×10−8 eV . 0.919 than the natural lifetime τ = 16 ns. For p =
2 938.8 ×106 10 mbar the second term becomes
The velocity of the H atom after emission of the
photon is: nσvr = 5.3 ×107 s−1
p k hν and the effective lifetime shortens to
v= = = c
m m mc2 τeff = 8.7 ns = 0.54 τn .
10.2
= × 3 ×10 8
m/s = 3.3 m/s .
9.38 ×108 For p = 100 mbar ⇒ τeff = 1.7 ns = 0.11 τn .
∆νrecoil v −8 9. The residual Doppler width in the collimated
⇒ = = 1.09 ×10
ν c atomic beam is
⇒ ∆νrecoil = 1.09 ×10−8 × 2.47 ×1015 s−1 a) (δνD )res = sin ε δνD < 190 MHz .
7 −1

= 2.7 ×10 s . With δνD = 7.16 ×10−7 ν0 T/M mol/(g K) = 2 ×
Chapter 7 535
109 s−1 with ν0 = 5.09 ×1014 s−1 , M = 23 g/mol, The absorption coefficient is
T = 695 K, v = 800 m/s 1
190 α = [N(F = 0) − N(F = 1)] · σabs
⇒ sin ε ≤ = 0.095 . 3
2000 = 0.006 · N(F = 0) · σabs .
b) If the residual Doppler width should be equal to
With σabs = 3 ×10−26 m2 , N = 106 m−3 and L =
the natural line width δνn = 10 MHz ⇒
3 ×1016 m we obtain
δνn 107
sin ε = = = 5 ×10−3 . α · l = 5.4 ×10−6 .
δνD 2 ×109
10. a) From the Einstein coefficient Aik = 3 × The absorption of the 21 cm line is therefore ne-
10−15 s−1 = τ1 we obtain the natural line width of gligible. For the Lyman α-line the situation is
the HFS transition with λ = 21 cm different:
Aik
δνn = = 5 ×10−16 s−1 . α = σ · N = 1 ×10−15 · 106 m−1 = 10−9 m−1 .
2π
The natural line width of the HFS transition is After 109 m the intensity has decreased to (1/ e)I0 .
therefore extremely narrow. The Doppler width is The interstellar cloud with L = 3 ×1016 m is
therefore completely opague. Lyman-α-light is
3 ×108 √
δνD = 7.16 ×10−7 10 s−1 = 3.2 kHz . completely absorbed.
0.21 c) The natural line width of the methane transition
The collision broadening is: is
nσvr 1
δνcoll = . δνn = s−1 = 7.96 s−1 .
2π 2π × 2 ×10−2

m1m2 This extremely small line width is used for stabi-
With vr = 8kT
πm = 460 m/s with m = m 1 +m 2
lizing the wavelength λ = 3.39 µm of the He-Ne
⇒ δνcoll = 7.3 ×10−20 s−1 . laser (see Chap. 8).
c
The collisional broadening is therefore completely δνD = 7.16 ×10−7 T/M(mol/(g K))
negligible. For the Lyman α-line we obtain: λ
Aik with λ = 3.39 µm, M = 16 g/mol, T = 300 K
δνn = = 1.6 ×108 s−1 ,
2π ⇒ δνD = 274 MHz .
δνD = 5.6 ×109 s−1 ,
δνcoll = 7.3 ×10−13 s−1 . The mean velocity of the CH4 molecules is

The Doppler width is by far the prominent 8kT
v= = 630 m/s .
broadening. πm
b) At a temperature T = 10 K the ratio of the
populations is ⇒ Transit time
0.01 m
N(F = 1) ttrans = = 1.6 ×10−5 s
= 3 · e−hν/kT ≈ 3 · 0.994 . 630 m/s
N(F = 0)
1
The population difference is ⇒ δνtrans = ≈ 104 s−1 .
2πttrans
1
∆N = N(F = 0) − N(F = 1) The only way to reduce transit-time broadening
3 is the enlargement of the laser beam diameter or
= 0.006 · N(F = 0) . a reduction of the velocity by cooling the gas.
11. According to (7.13) the matrix element for the with ∆m = +1, Mx − iM y with ∆m = −1 and Mz
transition 1s ↔ 2s is with ∆m = 0. The total transition probability is
proportional to
Mik = e ψ(2s)rψ(1s) dτ
|Mik | 2 = |(Mik )x | 2 + (Mik )2y + (Mik )2z ,
% %
1 % Mx + iM y % 2 = M 2 + M 2 .
= √ x y
4π 2a03 Using the wave functions of Table 5.2 we obtain:

r 1
× 2− e−r/(2a0 )r e−r/a0 dτ Mx + iM y = e−r/a0 (x + iy)r
a0 8πa04
r ϑ ϕ
r
=C 2− e−3r/(2a0 )r ×e −r/2a0
sin ϑ e−iϕ r 2 sin ϑ dϕ dϑ dr .
a0
r ϑ ϕ
With x = r sin ϑ cos ϕ; y = r sin ϑ sin ϕ one ob-
× r 2 sin ϑ dr dϑ dϕ , tains x + iy = r sin ϑ eiϕ

+π/2 2π ∞
r 1
(Mik )x = C 2− e−3r/(2a0 ) ⇒ Mx + iM y = r 4 e−3r/(2a0 ) dr
a0 8πa04
ϑ=−π/2 ϕ=0 r=0
× xr sin ϑ dr dϑ dϕ .
2 π 2π
× sin ϑ dϑ3
dϕ .
With x = r · sin ϑ cos ϕ the integration over ϕ yields
ϑ=0 ϕ=0
2π The first integral has the value 256 a05 /81, the se-
cos ϕ dϕ = 0 . cond integral is 4/3 and the third is 2π. This
ϕ=0 gives:
2
A similar result is obtained for (Mik ) y with y = 256
(Mx + iM y )2 = a0
r sin ϑ sin ϕ. For the third component (Mik )z we 243
obtain with z = r cos ϑ 3 2
2 e2 ωik a0 256 2
⇒ Aik (∆m = ±1) = .
2π 3 ε0 c3 h 243
dϕ = 2π With ωik = 2π 2.47 ×1015 s−1 the transition proba-
0 bility becomes:
but Aik (∆m = ±1) = 1.25 ×1010 s−1 .

+π/2 An analogous calculation for Mz with z = r cos ϑ
%+π/2
1 % gives
sin ϑ cos ϑ dϑ = sin2 ϑ % = 0.
2 −π/2 ∞
ϑ=−π/2 1
Mz = √ r 4 e−3r/(2a0 ) dr
12. The transition probability is, according to (7.17), 4π 2 a04
r=0
Aik (1s → 2 p) π 2π
%
3 %
% × cos ϑ sin ϑ dϑ
2
dϕ
2 e2 ωik %
= % ψ ∗ (2 p)rψk (1s) dτ % 2
3 ε c h
3 % i % ϑ=0 ϕ=0
0
1 256 5 2
The 2 p level has three components with m = 0, ±1 = √ 4 a0 2π
4π 2 a0 81 3
that are degenerate without external magnetic field.
256
There are therefore three degenerate transitions = √ a0
with different polarizations on the 1s → 2 p transi- 243 2
tion. If the quantization axis is chosen as the z-axis, 1
⇒ Aik (∆m = 0) = Aik (∆m ± 1) .
the matrix element Mx + iM y describes transitions 2
Chapter 8 537
13. The 3s level can only decay into the 2 p level. The- Since p = α(ω) · E we obtain for the polarizability
refore the transition probability for the transition
e2
3s → 2 p is α(ω) = * 2 + (4)
m ω0 − ω2 + iγω
1 109 −1
Aik = = s = 4.3 ×107 s−1 . The wave equation for a wave travelling through
τ(3s) 23
a medium is:
The natural line width is
∂2 E 1 ∂2 E
1 1 1 ∆E = µµ0 εε0 = , (5)
δνn = + ∂t 2 2 ∂t 2
vph
2π τ(3s) τ(2 p)
1 where
= 4.3 ×107 + 4.76 ×108 s−1
2π 1 c
vph = √ =√
= 83 MHz . µµ0 εε0 µε
The Doppler-width is is the phase velocity of the wave. In dielectric media
is the magnetic susceptibility µ ≈ 1 and we obtain:
δνD = 7.16 ×10−7 ν0 T/M[mol/(g K)] .
c c √
With vph = √ = ⇒ n = ε . (6)
ε n
1 ∗ 1 1 Inserting the relation: D = ε0 E + P into (1) we
ν0 = Ry − = 4.57 ×1014 s−1 ,
h 22 32 obtain the equation, equivalent to (5):
M = 1 g/mol , T = 300 K ,
1 ∂2 E 1 ∂2 P
∆E = + . (7)
this gives c2 ∂t 2 ε0 c2 ∂t 2
δνD = 5.67 ×109 s−1 = 5.67 GHz The dielectric polarization is for a wave with its
δνn E-vector in x-direction (E = {E x , 0, 0}):
⇒ = 0.014
δνD Px = N · α · E x = N · α · E 0 · ei(ωt−kz) , (8)
for T = 300 K and 0.008 for T = 1000 K.
where N is the number of oscillating dipoles per
14. The incident wave E 0 · ei(ωt−kz) induces the elec-
m3 and α is the polarizability.
trons of the medium to forced oscillations. If the
Inserting (8) into (7) gives:
amplitude of this oscillation is within the range of
linear optics (the restoring force is proportional to ω2 ω2 Nα
−k2 E x = − E x − Ex
the elongation of the atomic electron) we can des- c2 ε0 c2
cribe the atomic electron by a harmonic oscillator. ω2
Its equation of motion is: ⇒ k2 = (1 + Nα/ε0 ) (9)
c2
m ẍ + bẋ + Dx = −eE 0 ei(ωt−kz) . (1) with vph = c/n = ω/k ⇒ n = ck/ω, where n is the
refractive index.
With D/m = ω20 , γ = b/m we can make the ansatz
x = x0 eiωt . ⇒ n 2 = 1 + Nα/ε0 . (10)
Inserting this into (1) gives Inserting (4) into (10) yields
eE 0 /m Ne2
x0 = − 2 . (2) n2 = 1 + * 2 +.
ω0 − ω2 + iγω m ω0 − ω2 + iγω
The induced dipole moment p = p0 · eiωt with p0 = with n = n − iκ ⇒ n 2 = n 2 − κ 2 − 2in κ, where
e · x0 κ is the absorption coefficient and n the real part of
the complex index of refraction. For small dam-
e2 E
⇒ p= 2 . (3) ping (γω ω2 ) the summation over all atomic
m ω0 − ω2 + iγω resonances gives the result (7.102).
In order to transport a signal, the monochromatic where δν is the full half-width of the absorption
wave has to be modulated. The envelope of this profile. With αki = Nk σki we obtain:
modulated wave represents a wave packet with the
hν c2 Aik λ2 Aik
group velocity vg = dω/ dk. σki = Bki /δν = = .
c 8πν δν
2 8πδν
Inserting the Doppler width δνD ≈ 109 s−1 we
Chapter 8 obtain:
σki = 10−15 m2 = 10−11 cm2
1. a) The ratio of the populations Ni , Nk is:
⇒ A = 1010 × 10−11 × 1 = 0.1 .
Ni gi
= e−hν/kT This means that 10% of the incident light power is
Nk gk
gi = 2Ji + 1 = 3 , gk = 2Jk + 1 = 1 absorbed.
c) For the compensation of 10% total losses the
Ni
⇒ = 3 e−(hc/λ)/kT = 3 e−96 = 6.6 ×10−42 . condition −2αL ≥ 0.1 must be met.
Nk
The thermal population of the upper level |i is ⇒ (gk /gi )Ni − Nk σki L ≥ 0.05 .
therefore completely negligible. With gk = 1, gi = 3 and σki = 10−11 cm2 this gives:
b) The relative absorption of the incident wave with
1
intensity I0 is Ni − Nk 10−11 × 20 ≥ 0.05 .
I0 − It 3
A= , with
I0 With Nk = 1010 /cm3 the upper state population
It = I0 e−αL ≈ (1 − αL)I0 for αL 1 density then has to be
⇒ A ≈ αL = Nk σki L . Ni ≥ 3.075 ×1010 /cm3 .
The population density Nk = 10−6 N can be For equal statistical weight factors gi = gk the
obtained from the equation p = NkT minimum population Ni would be
⇒ Nk = 10−6 p/kT . Ni ≥ 1.025 Nk = 1.025 ×1010 cm−3 .
For a pressure p = 10 Pa we obtain:
2
This would require a population in the upper state,
10−6 × 102 which is 2.5% higher than in the lower state in order
Nk = m−3 to reach laser threshhold.
1.38 ×10−23 × 300
2. a) The Doppler width is
= 1016 m−3 = 1010 cm−3 .
c
The absorption coefficient α is related to the Ein- δνD = 7.16 T/M10−7 s−1 .
λ
stein coefficient Bki as follows: The absorbed power
With λ = 632.8 nm, T = 600 K, M = 20 g/mol this
is:
gives:
dWki
= Bki hν wν (ν) . δνD = 1.86 ×109 s−1 = 1.86 GHz .
dt
The spectral energy density wν (ν) is related to the b) The mode separation is
spectral intensity Iν (ν) by wν (ν) = Iν (ν)/c. The
power absorbed by one atom is c 3 ×108
δν = = = 150 MHz .
∞ 2d 2×1
1 dWki 1
= I(ν) α(ν) dν The number of longitudinal modes within the full
Nk dt Nk half-width of the Doppler profile is then
0
1 1.86 ×109
≈ I(ν0 )α0 (ν0 )δν , m= = 12 .
Nk 1.5 ×108
Chapter 8 539
3. a) The frequency separation of the transmission we obtain

maxima of the etalon is √
2 ∗ π F
c = 0.075 ⇒ F = = 28.5 .
δνE = . F 2
2nt
The finesse F ∗ must be at least 28.5 in or-
If this should be larger than the Doppler width
der to √select a single longitudinal mode. With
−7 c 5000 F ∗ = π R/(1 − R) we obtain for the reflectivity R
δνD = 7.16 ×10 = 5 ×109 s−1
λ 40 of the Fabry–Perot
at λ = 488 nm, the thickness t of the etalon should R > 0.89 .
be
c c 4. a) The frequencies νm of the resonator modes are
t= ≤
2nδνE 2nδνD c c
ν= =m· because L = mλ/2 .
3 ×108 λ 2L
= m = 2 ×10−2 m = 2 cm .
2 × 1.5 × 5 ×109 With L = 1 m, ν = 5 ×1014 s−1 ⇒ m = 3.33 ×106 ,
b) The intensity Iz transmitted through the Fabry– L = L 0 (1 + αT ) ,
Perot interferometer is:
∆L = L − L 0 = L 0 α∆T
1
It = I0 = 1 × 12 ×10−6 × 1 m
1 + F sin2 (π∆sν/c)
= 1.2 ×10−5 m ,
with F = 4R/(1 − R)2 . The finesse
√ √ ∆ν ∆L
π R π F ∆νm = = 1.2 ×10−5
∗
F = = = ν L
1− R 2 ∆νE ⇒ ∆ν = 1.2 ×10−5 × 5 ×1014 s−1
equals the ratio of frequency separation ∆νm of = 6 ×109 s−1 .
transmission maxima to the half-width ∆νE of the
transmission peaks. The transmission of the FPI has Since the mode distance is only ∆νL = 150 MHz
decreased from the maximum It = I0 to It = 13 I0 for the laser frequency jumps during the temperature
change after a shift of about ∆ν/2 ≈ 75 MHz back
F sin2 (π∆sν/c) = 2 to the next mode. Temperature tuning alone does
# $
π∆s not allow a continuous frequency shift of more than
= F sin2 (ν0 + ∆νL )
c 75 MHz, unless the resonator contains additional
frequency selective optical elements.
π∆s 2
⇒ sin ∆νL = . b) The refractive index n can be written as
c F
If ν0 is the frequency of the transmission peak, the n = 1 + aN ⇒ n − 1 ∝ N ,
condition where N is the number density of air molecules. If
sin (π∆sν0 /c) = 0 ⇒ π∆sν0 /c = m
2
(integer) the air pressure changes by ∆ p = 10 mbar = 1%,
the same relative change occurs for (n − 1). For air
must be met. For λ = 488 nm, ∆s = 2nt = 6 cm ⇒ at atmospheric pressure is n − 1 = 2.7 ×10−4 . The
m = 122,950. The frequency condition ∆νL of change for ∆ p = 1% is then ∆(n − 1) = 2.7 ×10−6 .
longitudinal modes is The optical path length inside the resonator changes
c then by
∆νL = = 125 MHz .
2d
∆(nL) = 2.7 ×10−6 × 0.2 m = 5.4 ×10−7 m
With
∆(nL)
π∆s 6π ⇒ ∆ν = ν0 = 2.7 ×108 s−1 .
sin ∆νL = sin 1.25 ×108 L
c 3 ×1010
Also in this case the laser frequency jumps back to
= 0.078 the next resonator mode, if ∆ν > ∆νm /2.
5. a) The classical diffraction theory yields for the Since a considerable fraction of the absorbed
diffraction of a plane wave with wavelength λ by energy is lost by heat conduction into the cold sur-
a circular aperture with diameter d the angular roundings, one needs, in fact, about ten times as
divergence of the central diffraction maximum long, i.e. t = 2.6 ms.
λ 6. a) The minimum spectral width is
∆α = 1.2 .
d ∆ν ≥ 0.5/∆T .
For a laser beam with a Gaussian intensity profile With ∆T = 10−14 s ⇒ ∆ν ≥ 0.5 ×1014 s−1 . For
with half-width w0 at the focusing lens with focal a wavelength λ = 600 nm this corresponds to
length f we obtain for the half-width of the local a spectral width
spot:
∆λ = 6 ×10−8 m = 60 nm .
λ
w0 = f . b) The spatial pulse length is in the beginning:
πws
With ws = d/2 we obtain: c∆T
∆s0 = = 2 ×10−6 m = 2 µm .
n
λ
w0 = f = 42 µm . After passing through a dispersive medium with
πd/2 length L, the pulse length has broadened. The
This differs from the result for a plane wave by the difference of optical path length for the different
factor 1.2π/2 ≈ 1.9. wavelengths λ within the spectral pulse profile is
b) The intensity is obtained from dn
∞ ∆(nL) = L ∆λ = L · 4.5 ×104 × 6 ×10−8
dλ
P = 2π r · I(r) dr = 2.64 ×10−3 L .
0 In order to keep ∆s ≤ 4 µm, the condition
∞
2 1
= 2πI0 · r · e−(r/r0 ) dr = πw20 · I0 ∆(nL) = (∆s − ∆s0 ) ≤ 2 µm
n
0
has to be fulfilled.
P 10 ×1012 W
I0 = = = 1.8 ×109 W/m2 . n 2.0 ×10−6 m
πw20 π · 422 m2 ⇒ L= = 1.1 ×10−3 m
2.64 ×10−3
c) Only 10% = 1 W can be used for the evapo- = 1.1 mm ,
ration. The mass of the evaporated material with
for n = 1.5. This means that after the passage
thickness D is
through a 1.1-mm thick glass plate the pulse length
M = · πw20 D has already doubled from 2 to 4 µm.
= 8 ×103 π × 422 × 10−12 × 10−3 kg c) Because of the nonlinear, intensity-dependent
part of the refractive index the wavelength λ is red-
= 4.4 ×10−11 kg . hifted during the pulse rise time (dI/ dt > 0). It is
The heat of evaporation is blue-hifted at the trailing edge (dI/ dt > 0).
If the material is chosen in such a way that the
We = 6 ×106 J/kg . linear part of n in the surrounding of λ0 (central
The necessary energy for evaporation is wavelength of the spectral pulse profile) shows an-
omalous dispersion (dn/ dλ > 0), the red part is
W = We · M = 2.6 ×10−4 J . delayed more than the blue part of the pulse. This
compensates the opposite effect of the nonlinear
The time needed for the evaporation of the mass M
part of n. Complete compensation demands
is:
d
t = W/P = 2.6 ×10−4 s = 0.26 ms . (n 0 (λ) + n 2 I ) = 0 .
dλ
Chapter 8 541
7. The resonator quality factor is defined as With a net gain −(2αd + γ) = 0.05 we obtain
Wk P1
Q k = −2πν , = e0.05 = 1.05 .
dWk / dt P0
where The time T for a round trip is
2d 2
Wk (t) = Wk (0) e−γk t T= = 10−8 s .
c 3
is the energy stored in the kth mode of the resonator. The time-dependent power then becomes:
If γk are the losses per round trip, the power after # $
2αd + γ
one round trip has decreased to P(t) = P0 exp − t .
2d/c
P = P(0) e−γL . With a mirror transmission T = 0.02 the output
power of 1 mW demands a power of 50 mW inside
The loss factor γL is composed of reflection
the resonator. The initial power P(0) is given by
losses and other losses (diffraction, scattering,
one photon, i.e.,
absorption). The reflection losses per round trip are
hνc
γ R = − ln(R1 R2 ) = 0.02 . P(0) = = 4.5 ×10−10 W .
2d
If the other losses together are also 0.02, we obtain a)
P −8
γL = 0.04 . = e0.05/(0.666×10 s)t
P0
Since the round trip time of a light wave in 1s P
⇒ t= ln
a resonator with mirror separation d is 7.5 ×106 P0
5 ×10−2
T=
2d = 1.3 ×10−7 ln s
c 4.5 ×10−10
= 25 ×10−7 s = 2.5 µs .
the losses per sec and are
c b) If we take into account saturation effects, the gain
γ = γL /T = γL . depends on the laser power inside the resonator. We
2d
obtain:
With d = 1 m ⇒ γ = 1.5 ×108 × 0.04 s−1 = 6 × dP(t) gain per round trip
106 s−1 . The quality factor is then for a frequency = P(t)
dt round trip time
ν = 5 ×1014 s−1 :
1* +
2π 5 ×1014 = − (−2α0 d + γ) − 2adP(t) P(t) .
Qk = = 5.2 ×108 . T
6 ×106 With T = 2d/c, (−2α0 d + γ) = 0.05 this gives
Per oscillation period of the light the power dP 1
decreases by the fraction = (0.05 − 2adP)P .
dt T
2π This is a nonlinear differential equation
η= = 1.2 ×10−8 .
5.2 ×108 ẏ − Ay + By2 = 0
−7
It takes 1/γ ≈ 1.7 ×10 s until the power in the
with
resonator mode has decreased to 1/ e of its initial
0.05 2ad
value. A= , B= .
8. After one round trip the power has increased by the T T
factor Division by y2 gives:
P1 ẏ A
= e−(2αd+γ) . − +B = 0.
P0 y2 y
Substitution: Chapter 9
1 1
z(t) = ⇒ ż = − 2 ẏ ,
y(t) y 1. The potential energy of the Coulomb repulsion of
⇒ ż + Az − B = 0 . the two protons is
The solution of the homogeneous equation (B = 0) e2

E pot = = 2.3 ×10−18 J = 13.6 eV .
gives: 4πε0 · 2a0
z = C e−At . The potential energy of the electron in the state
|φ+ is
The solution of the inhomogeneous equation
e2 % +% 2 1 1
(B = 0) is: E pot = − %φ % + dτ .
4πε0 rA rB
z = C(t) e−At ⇒ ż = Ċ − C A e−At .
The wave function is
Inserting this into the inhomogeneous equation φA + φB
yields φ+ = √
2 + SAB
Ċ − C A + AC = B e At Inserting φA and φB from (9.9) gives:
B
⇒ C = e At + D % +% 2 1 e−2rA /a0 + e−2rB /a0 + 2 e−(rA +rB )/a0
A %φ % =
B 2πa03 1 + SAB
⇒ z = + D e−At 2
A e
1 E pot = − 2 3
⇒ y= 8π ε0 a (1 + SAB )
B/A + D e−At # −2rA /a0 0 −2rB /a0
e +e + 2 e−(rA +rB )/a0
1
⇒ P(t) = . rA
2ad/0.05 + D e−0.05t/T $
e−2rA /a0 + e−2rB /a0 + 2 e−(rA +rB )/a0
For t = 0 ⇒ P = P0 + dτ .
rB
1
⇒ D= − 40ad With elliptical coordinates
P0
P0 rA + rB
⇒ P(t) = . µ= ;
40adP0 + (1 − 40adP0 ) e−0.05t/T R
rA − rB
With P(t1 ) = 50 mW ⇒ P(t1 )/P0 ≈ 108 because ν= ;
R
P0 = 4.5 ×10−10 W. The denominator therefore has ϕ = arctan (y/x)
to be 10−8 . With a = 0.4 W−1 m−1 , d = 1 m we
obtain where the two protons are sitting in the focal points.
With these coordinates and
40 × 0.4 × 4.5 ×10−10 + e−0.05t/T = 10−8
R3 2
⇒ e−0.05t/T = 2.8 ×10−9 dτ = µ − ν2 dµ dν dϕ ,
8
T
⇒ t=− ln 2.8 ×10−9 the integral can be solved analytically. With
0.05
T R
⇒ t=+ ln 3.57 ×108 rA = (µ + ν) ,
0.05 2
= 20 T 19.7 = 394 T . R
rB = (µ − ν) ,
2
With T = 23 10−8 s ⇒ 263 ×10−8 s = 2.63 µs. With the overlap integral SAB becomes:
a = 0.55 W−1 m−1 t increases to
1
t = 20 T ln 1010 s = 30.7 µs . SAB = 3 e−(rA +rB )/a0 dτ
πa0
Chapter 9 543
⎡
∞ +1 2π For = 2 ⇒ SAB = 0.586 ⇒
3
R ⎢
= ⎣ µ2 · e−Rµ/a0 dµ dν · dϕ e2
8πa03 2Ca02 =
µ=1 ν=−1 ϕ=0 4πε0 a0 · 1.586
⎤ 27.2 eV
∞ 1 2π ⇒ E pot = − · 1.879 = −32.2 eV .
⎥ 1.586
− e−Rµ/a0 dµ ν2 dν dϕ⎦ .
The kinetic energy of the electron can be obtained
µ=1 ν=−1 ϕ=0
from the energy relation
The integration yields E kin ( e− ) + E pot ( e− ) + E pot (protons)
= E(H) + E B ,
R R2
SAB = e−R/a0 1 + + 2 .
a0 3a0 where E B is the binding energy of H+2 and E(H) is
the energy in the groundstate of the H-atom.
This gives for the potential energy
⇒ E kin ( e− ) = −13.6 eV − 2.65 eV + 32.2 eV

C · R2 − 13.6 eV
E pot = − e−(µ+ν) + e−(µ−ν)
2π = 2.35 eV
µ ν ϕ

+ e−µ µ dµ dν dϕ This approximate method gives a too small va-
lue. The real value is E kin = 12 eV, compared to
with E kin (H) = 13.6 eV.
2. For R → 0 the H2 -molecules converge towards the
e2 He-atom 22 He. Therefore the energy of the electrons
C= ; = R/a0
8πε0 a03 (1 + SAB ) has to converge towards the groundstate energy of

the He-atoms. (Note that the two missing neutrons
⇒ E pot = −C · R2 µ e−(µ+ν) + e−(µ−ν)
do not affect this energy.) This is, according to
µ ν
Sect. 6.1:
+ e−µ µ dµ dν
E(He) = −78.9 eV .
∞
= −C · R2 µ e−µ dµ This value can be composed of the energy
µ=1 E 1 = −2 × 4 × 13.6 eV = −108.8 eV
+1
without repulsion between the two electrons, and
× e−ν + e+ν + 1 dν the Coulomb energy
ν=−1
# $
1 E 2 = +29.9 eV
= −2C R2 1 + e − e−
of this repulsion.
∞ The energy of the electron is:
× µ · e−µ dµ e2
E el (H2 , R = Re ) = 2 · E(H) + E B (H2 ) − ,
1# $ 4πε0 Re
1
where E(H) = −13.6 eV is the electronic energy
= −2Ca02 1 + e − e−
of the H-atom, E B (H2 ) = −4.7 eV is the binding
−
× ( + 1) e energy of the H2 -molecule and e2 /(4πε0 Re ) =
#
1 0.3 ×10−17 J = 19.4 eV is the nuclear Coulomb re-
= −2Ca0 1 +
2
1 − e−2 pulsion at a distance Re = 0.074 nm between the

$ two protons. The result is:
−
+ (1 + ) e .
E el (H2 , R = Re ) = −51.1 eV .
This energy is composed of negative potential and the vibrational-rotational energy is then
energy, due to electron–proton attraction, positive ∞
)
potential energy of electron–electron repulsion and E vib, rot = N(v, J ) · E(v, J )
positive kinetic energy of the two electrons. v,J=0

3. a) The total energy of the rigid H2 -molecule (inclu- 1
ding Coulomb repulsion between the two nuclei) with E vib = n + · ωvib ;
2
is, according to (9.2) E rot = J(J + 1)hc · Brot .
E(H2 ) = 2E(H) + E B (H2 ) The results do not differ much from the estimation
above.
= −27.2 eV − 4.7 eV 4. In the product
e2
= E el (H2 , Re ) + ψ (r, R) = χ(R) · ψel (r, R)
4πε0 Re
of nuclear wave functions χ(R) and electronic wave
⇒ E el (H2 , Re ) = −19.4 eV − 31.9 eV function ψel (r, R) the parameter R is not a variable.
= −51.3 eV . The wave function ψ(r, R) is a function of r, which
can be calculated for any arbitrary but fixed value
In order to separate the H2 -molecule into 2 elec- of R.
trons and 2 protons one has to put the energy The Schrödinger equation is:
E = E el (H2 , Re ) − e2 /(4πε0 Re ) = 31.9 eV into the
2 )
2
molecule. − ∆k (χ · ψel ) (1)
b) At a temperature of 300 K the mean vibrational 2M k=1
energy is: E vib = kT (potential + kinetic energy of 2
the vibrating nuclei). The rotational energy (2 de- − ∆e (χ · ψel ) + E pot · χ · ψel = Eχψel .
2m e
grees of freedom for rotations around two possible
Multiplying the equation with ψel∗ and integrating
axis perpendicular to the internuclear axis) is
over the electron coordinates, gives with

1 ψel∗ ψel dτ = 1
E rot = 2 · kT = kT
2
⇒ E vib + E rot = 2kT . the equation:

2 )
2
∗
2
The relation between kT and E is: − ∆k χ − ψel ∆e ψel dτel · χ
2M k=1 2m e

1 eV =
ˆ kT for T = 11,604 K . + χ · ψel∗ E pot ψel dτ = E · χ
⇒ at T = 300 K: because the operator ∆k acts only upon χ and ∆e
only upon ψel .
300 The time-averaged potential energy of the nuclei,
2kT =
ˆ 2· eV = 52 meV .
11.604 averaged over the motion of the electron is
1 2 2
This is very small compared to the electronic energy el 6 el 7 e
E pot (R) = E kin + E pot +
difference E el ≈ 10 eV between the first excited 4πε0 R

electronic state and the groundstate of H2 . 2
The correct calculation of E vib and E rot has to take = − ψel∗ ∆e ψe dτe
2m
into account the quantization of the energy levels. e
∗ e2
The population of a level (v, J ) is: + ψel E pot +el
ψel dτel
4πε0 R
(2J + 1) e−(Erot +Evib )/kT 2 )
N(v, J ) = (∞ ⇒ − ∆k χ + E pot (R) χ = Eχ .
−(E rot +E vib )/kT
v,J=0 (2J + 1) e
2M k
Chapter 9 545
The equation for the electrons

( innucl
the rigid molecule of molecular vibrations around the equilibrium
is obtained from (1) with k E kin = 0. distance Re we obtain:
5. The Schrödinger equation (9.80) is for the non-
rotating molecule (J = 0), M = M1 − M2 /(M1 + 1 h 2 c2 ω2e 1 2
E(v) = h · c · ωe v + − v+ .
M2 ): 2 4E D 2

1 d 2 dS 2M * + For the harmonic oscillator the second term is zero.
R + 2 E − E pot (R) S = 0 . (2) This quadratic term has the consequence, that the
2
R dR dR
vibrational energy levels are no longer equidistant,
Introducing the function χ(R) = R · S(R) (2) be- but the distance ∆E = E(v + 1) − E(v) decreases
comes: with increasing v.
d2 χ 2M * + For
+ E − E pot (R) χ = 0.
dR2 2 1
hcωe v + = 2E D
With the relative elongation = (R − Re )/Re of 2
the vibrating nuclei and the Morse-potential the dissociation limit is reached. The maximum
2 possible quantum number v is then:
E pot (R) = E D 1 − e−a
2E D 1
we obtain: vmax = − .
hcωe 2
d2 χ 2M
−a 2
+ E − E D 1 − e χ = 0. (3) 6. The ionization energy of H2 is (Fig. S.12):
dR2 2

With the trial solution: E ion (H2 ) = E B (H2 ) + E ion (H) − E B H+
2
√
χ=zA 1−ε −z/2
e ·u , = (4.48 + 13.6 − 2.65)eV
E = 15.43 eV . (4)
z = 2A · e−a ; ε= ,
ED The binding energies E B (H2 ) and E B (H+
2)are de-
2E D · MRe2 fined as the energies from the minimum of the
A =
2
2 a2 potential curve to the dissociation limit. The mea-
Equation (3) becomes the Laguerre differential sured values of the dissociation energy refers to
equation: the lowest vibrational level. In this case the energy
/ √ 0 relation is:
d2 u du 2A 1 − ε + 1
+ −1 E ion (H2 , v = 0) = E D (H2 , v = 0) + E ion (H)
dz 2 dz z
√ − E D H+ 2 ,v = 0 , (5)
A − 12 − A 1 − ε
+u · = 0.
z
This equation has the eigenvalues (see text books
on differential equations)

v + 1/2 2
ε = 1− 1−
A

2 1 1 1 2
= v+ − 2 v+ ,
A 2 A 2
where v = 0, 1, 2 is the vibrational quantum
number. With the vibrational frequency
2E D
ωe =
hc · A Fig. S.12.
which differs from (4) by the difference of the zero- With E pot = k · (R − Re )2
point energies
⇒ R − Re = E pot /k .
∆E ZP = E vib (H2 , v = 0) − E vib H+ +
2 ,v = 0 . The energy of the vibrational level v = 1 is
3
7. With Re = 1.2745 Å ⇒ E vib = h · ν .
2
At the turning point is E kin = 0 ⇒ E vib = E pot =
Be = , 3
4πcµRe2 2 hν
m1 · m2 3
µ= ⇒ k·(R − Re )2 = h · ν
m1 + m2 2
1 · 35 8 1/2
= = 0.9722 AMU for H35 Cl 3 −34
36 ⇒ R − Re = · 6.6 ×10 · 9 ×10 13
513
2
1 · 37
= = 0.9737 AMU for H37 Cl = 1.32 ×10−11 m = 0.132 Å .
38
The vibrational amplitude in the level v = 1 is
⇒ Be H35 Cl = 10.68 cm−1 , therefore only about 10% of the internuclear
37
⇒ Be H Cl = 10.659 cm−1 . distance Re :
For H35 Cl we obtain: (R − Re )/Re 0.104 .
νrot (J = 0 → J = 1) = 2cBe
= 6 ×1010 · 10.68 s−1 = 64.1 ×1010 s−1 Chapter 10
= 641 GHz ,
νrot (J = 4 → J = 5) = 10cBe 1. The three principal rotational axes are perpendi-
= 3204 GHz = 3.204 THz . cular to each other and intersect in the center of
mass S (Fig. S.13), which divides the heights h of
For H37 Cl we obtain: the triangle in the ratio 2 : 1. If the sides of the tri-
νrot (J = 0 → J = 1) = 6 ×1010 · 10.66 s−1 angle are denoted as s we obtain the three moments
of inertia for rotations around the axis i:
= 639.6 GHz ⇒ λ = c/ν = 4.7 cm , 2 2
h 2h
∆νrot H35 Cl − H37 Cl = 1.4 GHz Ia = I1 = 2m +m
3 3
νrot (J = 4 → J = 5) = 3.198 THz 2 2 2 2
⇒ λ = 0.94 cm . = mh = ms cos2 (α/2) ,
3 3
The rotational energy E rot (J = 5) is: where m is the mass of the Na-atom.
E rot /hc = J · (J + 1) · Be = 30 Be Ib = I2 = 2mx 2 = 2ms2 sin2 (α/2)
2
= 320.4 cm−1 ⇒ E rot = 39.7 meV for H35 Cl Ic = I3 = 2mr 2 + m
2
h
= 319.8 cm−1 ⇒ E rot = 39.6 meV for H37 Cl 3
8. The vibrational frequency for the model of

a harmonic oscillator is:
1
ν= k/µ ⇒ k = 4π 2 ν2 · µ .
2π
For H35 Cl is µ = 0.9722 AMU
⇒ k = 4π 2 · 9 ×1013 · 0.9722 · 1.66 ×10−27 kg/s2
= 513 kg/s2 . Fig. S.13.
Chapter 10 547
h 2
with r 2 = x 2 + 3 we obtain:
2
I3 = 2mx 2 + mh 2
3
1
= 2ms sin (α/2) + cos (α/2) .
2 2 2
3
For α = 80◦ this gives:
I1 = 0.39 m · s2 ; I2 = 0.83 m · s2
I3 = 1.22 m · s2
⇒ I3 = I1 + I2 .
The last equation is true for all planar molecules.
The Na3 -molecule represents an asymmetric rotor Fig. S.14.
with I1 = I2 = I3 = I1 .
With m = 23 × 1.66 ×10−27 kg; s = 3.24 Å =
3.24 ×10−10 m x = s · sin(α/2)
⇒ Ia = 1.56 ×10−45 kg m2 Ia = 2m(0)y12 + m(N)y22
2 !
Ib = 3.32 ×10−45 kg m2 = y12 2m(O) + m(N)
32
Ic = 4.85 ×10−45 kg m2 14
= (32 + 73) AMU · y12
The rotational constants are defined as:
= 105 AMU y12 = 1.74 ×10−25 kg · y12
A= = 17.85 m−1 = 0.1785 cm−1
4πc · Ia Ib = 2m(O) · x 2 = 2m(O) · s2 · sin2 (α/2)
= 32 AMU · s2 sin2 (α/2)
B= = 8.388 m−1 = 0.0839 cm−1
4πc · Ib = 0.53 ×10−25 kg · s2 · sin2 (α/2)

C= = 5.742 m−1 = 0.0574 cm−1 Ic = m(N) · y22 + 2 x 2 + y12 · m(O)
4πc · Ic
= 14y22 + 32 x 2 + y12 AMU · m 2 .
One can prove, that within the accuracy of rounding
up and down the relation Replacing x by x = s · sin(α/2); y2 by y2 = y −
1 1 1 y1 = s · cos(α/2) − y1 we have 3 equations for 3 un-
= = known parameters s, α and y1 , since the moments of
A B C
inertia are known. They can be solved numerically
is valid for the planar Na3 -molecule. This is,
and give:
however, only strictly valid for the non-vibrating
molecule. s = 0.119 nm
2. The values of the moments of inertia can be
α = 134◦
obtained from the rotational constants.
y1 = 0.017 nm .

Ia =
4πc · A 3. The linear molecule C2 H2 with 4 atoms has 3 ·
and corresponding expressions for Ib , Ic . From 4 − 5 = 7 normal vibrations, where the two vibra-
Fig. S.14 we find: tions ν4 and ν5 are degenerate (Fig. S.15). There
are therefore 5 different vibrational frequencies
y1 m(N) 14
= = = 0.438 ν1 , ν2 , . . . , ν5 . Transitions from the (0, 0, 0, 0, 0)-
y2 2m(=) 32
vibrational ground state to excited vibrational states
y = y1 + y2 = s2 − x 2 are infrared active, if the dipole moment of the up-
Fig. S.15.
Fig. S.17.
Fr = −1.3 ×10−8 N. For the bending vibration ν2

the amplitude ∆y of the C-atom is
2m(O) 32
∆y1 (C) = − · ∆y2 (O) = − ∆y2 .
per state is different from that of the ground state. m(C) 12
These are the vibrations ν3 and ν5 . The time dependent distance d(t) between the C-
The Raman active transitions are: ν1 , ν2 and ν4 atom and one O-atom of the vibrating molecule is
(Fig. S.15). (Fig. S.17):
4. In the approximation of harmonic oscillations the * +1/2
frequencies ν are related to the force constants k by d = d02 + (∆y1 − ∆y2 )2
* +1/2
1 = d02 + (1.375 ∆y1 )2
ν= k/µ ,
2π !1/2
∆y1 2
where µ is the reduced mass. = d0 1 + 1.9
d0
For the normal vibration ν1 the C-atom remains at / 0
rest and the two O-atoms oscillate with opposite ∆y1 2
phases (Fig. S.16). The restoring forces for the two ≈ d0 1 + 0.95 .
d0
C−O bonds are equal with opposite directions. The
reduced mass is The change (d − d0 ) during the bending vibration
2m(O) · m(C) 2 · 16 · 12 is then
µ= = AMU
2m(O) + m(C) 44 d − d0 = 0.95∆y12 /d0 .
= 8.73 AMU .
The restoring force is
The restoring force constant k1 is then:
F = −k2 (d − d0 ) = −k2 · 0.95∆y12 /d0 .
k1 = 4π 2 ν12 · µ = 4π 2 c2 ν21 µ
The energy is then
= 4π · 9 ×10 · 1388 × 8.73 AMU
2 20 2
1
= 9.96 ×102 kg/s2 ≈ 1000 kg s−2 . E vib = h · ν = h · ν · c = 2 · · k2 (d − d0 )2 .
2
The restoring force Fr = −k · (R − Re ) at the maxi- On the other side is
mum elongation (R − Re ) = 1.3 ×10−11 m is then
k2 = 4π 2 c2 ν22 · µ = 231 kg s−2 .
This gives a change
d − d0 = (hν · c/k2 )1/2
Fig. S.16. = 7.6 ×10−10 m = 0.076 Å .
Chapter 11 549
This should be compared with the average distance Chapter 11

d0 ≈ 1.2 Å. The vibrational amplitude is therefore
only 6% of the C−O-distance. 1. The net absorption coefficient α is, according to
5. a) The ground state configuration of BH2 is (11.2) given by
. . . (2a1 )2 (1b2 )2 (3a1 )1 X 2 A1 . According to the * +
Walsh diagram in Fig. 10.11 the energy of the (2a1 )- α = Nk − (gk /gi )Ni σki . (1)
orbital and of the (1b2 )-orbital decreases from In our case is
α = 90◦ to α = 180◦ , while that of the (3a1 ) stron-
gly increases. The total energy has a minimum gk = 2Jk + 1 = 3 ; gi = 2Ji + 1 = 5 .
(from an estimation of the curves in Fig. 10.11)
The transition wave number is
at α ≈ 125◦ –135◦ . The correct value is α = 131◦ .
b) In the first excited state the electron in the ν = B e [Ji (Ji + 1) − Jk (Jk + 1)]
(3a1 )-orbital is excited into the (1b1 )-orbital. = 4Be = 42.36 cm−1 .
The energy of this orbital is independent of α
and therefore the excited state leads to a li- The frequency of the absorption line is:
near configuration (α = 180◦ ) which is labelled as ν = c · ν = 1.27 ×1012 s−1 .
(2σg )2 (2σu )2 (1πu )1 A2 πu .
6. In the approximation of the Morse-potential the In this case is h · ν kT
energy levels are
Ni Nk −hν/kT Nk hν
* + ⇒ = ·e ≈ 1−
E(v) = h · c · 15.5ωe − ωe xe (15.5)2 gi gk gk kT

= hc 2176.2 cm−1 hν
⇒ α ≈ Nk σki . (2)
kT
= 4.3 ×10−20 J = 0.27 eV .
At a pressure p = NkT the density of molecules is
The energy difference between neighbouring N = p/kT . With p = 1 mbar = 102 Pa
vibrational levels is:
102 m−3
∆E = E(v = 15) − E(v = 14) ⇒ N= .
1.38 ×10−23 · T/K
= hc[ωe − 30ωe xe ]
* + * + For T = 100 K ⇒ N = 7.25 ×1022 m−3 . The po-
= hc (159 − 36) cm−1 = hc · 123 cm−1 pulation density of the absorbing level Nk (Jk ) is
= 0.015 eV . then:
The Fourier-limited frequency width of the 30 fs (2Jk + 1) · N −Erot /kT
Nk (Jk ) = ·e , (3)
laser pulse is Z
1 where
∆ν = ≈ 15.8 ×1012 s−1 )
2π∆t Z= gn e−En /kT
⇒ ∆E = h · ∆ν = 11.5 ×10−21 J n
−2
= 6.3 ×10 eV = 0.063 eV . is the partition function,
( which is a normalization
Therefore about 4–5 vibrational levels are simulta- factor, that assures n Nn = N.
nously excited. For v = 15 the nuclear vibrations For
can be treated classically. ∆E rot = E rot (J + 1) − E rot (J ) kT
* +
⇒ ∆E = h · νvib = hc · 123 cm−1 we can approximate the partition function Z by the
⇒ νvib = 3 ×1010 · 123 s−1 integral over a continuous variable J:
= 3.7 ×1012 s−1 ∞
kT
1 Z ≈ (2J + 1) e−hc·Be J(J+1)/kT dJ = .
⇒ Tvib = = 2.7 ×10−13 s = 270 fs . hcBe
νvib 0
For our example of the HCl-molecule is Jk = 1, 3. The grating equation is

Be = 10.59 cm−1 and Z = 6.56 ×10−2 · T/K. For
T = 100 K this becomes Z = 6.56 and the ratio d(sin α + sin β) = λ .
Nk 3 For our example is
≈ · e−0.3 ≈ 0.34 .
N 6.56 1
d= mm = 0.833 µm ,
This means that 34% of all molecules are in the 1200
level with Jk = 1. 1
α = 30◦ ⇒ sin α = ,
Inserting (3) in (2) gives 2
1 588.9
(2Jk + 1)h 2 cνBe −Erot /kT sin β1 = − + = +0.2067
α= e ·σ · N . 2 833.3
(kT)2
⇒ β1 = 11.93◦ = 0.2082 rad ,
With the numerical values: N = 7.25 ×1018 m−3 , 1 589.5
Be = 1059 m−1 , Jk = 1, T = 100 K one abtains sin β2 = − + = 0.2074 rad
2 833.3
α = 1.9 ×10−3 m−1 . ⇒ β2 = 11.97◦ = 0.2089 rad .
For T = 300 K the absorption coefficient becomes The angular difference is
α = 2.1 ×10−4 m−1 . ∆β = 0.04◦ = 7.36 ×10−4 rad .
2. The two functions In the focal plane of the imaging mirror with focal
length f = 1 m is the lateral distance between the
+∞ two spectral lines:
1
f(t) = √ g(ω) · e−iωt dω
2π ∆s = f · ∆β = 1 · 7.36 ×10−4 m = 0.736 mm .
−∞
+∞ With a slitwidth d < 360 µm of the entrance slit the
1
g(ω) = √ f(t) · e+iωt dt two lines can be separated.
2π 4. a) The shift of the Raman line against the Rayleigh
−∞
line is for ∆v = 1, ∆J = 0 for the H2 -molecule
form a Fourier-pair. With the relation ∆ν = 4395 cm−1 . The wave number of the argon-
eiωt = cos ωt + i sin ωt ion laser line is
107
the real cosinus-Fourier-transform of gc (ω) is νL = = 20,492 cm−1
488
∞
2 ⇒ νR = (20,492 − 4395)cm−1 = 16,097 cm−1
f c (t) = gc (ω) cos ωt dω
π ⇒ λR = 490.9 nm .
0
∞ b) The term value of the rotational level J = 1 is
2 with Be = 60.8 cm−1
gc (ω) = f c (t) cos ωt dt .
π
0 T(J = 1) = J · (J + 1)Be = 121.6 cm−1 .
The computer, used to perform these transformati- The difference between the Rayleigh and Raman
ons in Fourier-Sepctroscopy subtracts the constant line is
background term in (11.74a), which is √independent
of the time t. Substituting f c (t) by π/2S(t) and ∆ν = 121.6 cm−1 ⇒ ∆λ = λ2 · ∆ν = 2.9 nm .
¯ · v/c) one obtains
gc (ω) by I(ω
The spectral resolving power of the spectrometer
∞ should be at least
¯ · v/c) =
I(ω S(t) cos(ω · v/c) dt . λ 488
R≥ = = 168 ,
0 ∆λ 2.9
Chapter 11 551
which can be achieved already with a small grating must be fullfilled. This gives
or prism spectrometer.
sin ε < 0.11 ⇒ ε < 6.4◦ .
5. According to Beer’s absorption law the transmitted
laser power is b)
−αx 16
Pt = P0 · e ≈ P0 (1 − αx) for αx 1 . sin ε < = 9.4 ×10−3 ⇒ ε = 0.55◦ .
1700
The power, absorbed per cm path length is Here one has to take into account, that the natural
∆P = α · P0 = 10−6 · 10−1 W = 10−7 W . line width is already ∆νn = 10 MHz. The absorp-
tion profile is the convolution of Lorentzian and
For a wavelength λ = 500 nm is Gaussian profiles and the total linewidth is

h · ν = 2.48 eV = 3.97 ×10−19 W s . ∆ν ≈ ∆νn2 + (∆νD sin ε)2
The absorbed power ∆P corresponds to 1/2 −1
⇒ ∆νD · sin ε ≤ (∆ν)2 − ∆νn2 s

∆P 10−7 W = 10 · (16)2 + (10)2 s−1
6
N= = √
h · ν 3.97 ×10−19 W s = 106 · 156 s−1
= 2.5 ×1011 absorbed photons/s
≤ 12.5 MHz
which generate 2.5 ×1011 fluorescence photons. 12.5 ×106
The photo detector receives ⇒ sin ε ≤ = 0.0074
1700 ×106
◦
∆Ω 0.2 ⇒ ε ≤ 0.43 .
·N = · 2.5 ×1011 = 4 ×109 photons/s .
4π 4π 7. a) The transverse force Fx acting on the atoms
With a quantum efficiency η = 0.2 of the detector flying into the z-direction is
this gives 0.2 · 4 ×109 = 8 ×108 photo-electrons/s.
If the amplification of the photomultiplier is G = Fx = − | pm · grad B| .
106 the output current is The magnetic moment in the 2S1/2 state is mainly
due to the electron spin, i.e. pm = µB = 9.27 ×
IA = 8 ×108 · 1.6 ×10−19 · 106 = 0.13 mA .
10−24 J/Tesla. The deflection angle α of the sodium
6. With a collimation angle ε = 2◦ the residual atoms is
Doppler width of an absorption line is vx
tan α = .
vz
∆νD (beam) = sin ε · ∆νD (cell) .
The velocity vx is after a flight time t = L/vz
For a temperature T is t µB L
vx = µB · |grad B| · = |grad B| ·
−7
∆νD (cell) = 7.16 ×10 ν0 T/M . m m vz
For α = 3◦ ⇒ tan α = 0.052. With L = 0.2 m, vz =
With T = 500 K, M = 23 g/Mol, ν0 = 5.09 ×
600 m/s ⇒ vx = 0.052 · 600 m/s
1014 s−1
m · v x · vz m · v2z tan α
⇒ ∆νD = 1.7 ×109 s−1 ⇒ grad B = =
µB · L µB · L
⇒ ∆νD (beam) = (sin 2◦ ) · 1.7 ×109 s−1 23 · 1.66 ×10−27 ·36 ×104 · 0.052
=
= 5.9 ×107 s−1 . 9.3 ×10−24 · 0.2
= 3.8 ×10 T/m .
2
a) In order to resolve the hyperfine structure of the
3 2P1/2 level, the condition b) The photon transfers the momentum

∆νD (beam) = 1.7 ×109 · sin ε s−1 < 190 MHz ∆ p = h · ν/c .
The momentum of the sodium atoms in z-direction The mean relative velocity vr is
is
2 · 8 kT
pz = m · vz . vr =
π ·m
m1 · m2 23 · 28
The deflection angle for the absorption of one with m = = = 12.6 AMU
m1 + m2 51
photon is √
π · m · kT
∆p h ·ν ⇒ p=
tan α = = 4σ · τspont
pz c · m · vz √
with h · ν = 2.1 eV . π · 12.6 · 1.66 ×10−24 · 1.38 ×10−23 · 400
= Pa
4 · 10−19 · 1.6 ×10−8
For n absorbed photons it is: = 0.93 ×105 Pa = 0.93 bar .
h ·ν
tan α = n · . 9. Assume the level E i is selectively excited by a cw
c · m · vz laser with an excitation rate Rexc . If the total
In order to reach a deflection of α = 3◦ one needs deactivation rate is
c · m · vz
n= · tan α D = Ni Ai + n · σq · v ,
h ·ν
3 ×108 · 23 · 1.66 ×10−24 · 600 where n is the density of collision partners. We ob-
= tain D = R under stationary conditions. This yields
2.1 · 1.6 ×10−19
= 1 ×10 photons ,
3 the stationary population density
D R
With a laser beam diameter d = 1 cm the time of Ni = = ,
flight of the atoms through the laser beam is Ai + n · σq · v Ai + nσq v
where σq is the total deactivation cross section for
t = d/vz = 1.6 ×10−5 s . nonradiative transitions. The fluorescence power,
The minimum absorption rate is then emitted by level E i is

Rabs = n/t = 103 / 1.6 ×10−5 = 6.3 ×107 s−1 , Pi = Ni · Ai .
which implies that the mean cycle time absorption- If level E m is populated by collisional energy
fluorescence should be τc = 1/Rabs = 16 ns. The transfer from level E i we obtain:
spontaneous life time is τsp = 16 ns. Since the mi- dNm
nimum mean cycle time is τc ≈ 2 τsp the maximum = n i · n · σi→m · v − Nm · Am = 0
dt
rate can be only Rmax = 3.15 ×107 s−1 . The la- Nm A m
ser beam diameter therefore has to be enlarged to ⇒ σi→m = ·
Ni n · v
d = 2 cm. Pm Ai
8. The effective life time is = · .
Pi n · v
1 1
= + n · σ · vr . Measuring the relative total fluorescence powers
τeff τspont Pm /Pi yields σi→m , if Ai = 1/τi is known from
If τeff = 12 τspont we obtain lifetime measurements of level E i .
1
n · σvr = .
τspont Chapter 12
With p = n · k · T ⇒
1. The lifetime of the 3 2P3/2 level is τ = 16 ns,
p · σ · vr 1 k·T
= ⇒ p= . the optimum absorption-emission cycle pe-
k·T τspont σ · vr · τspont riod is 2τ = 32 ns, the absorption rate R =
Chapter 12 553
1/(2τ) = 109 /64 ≈ 1.6 ×107 s−1 . Each absorbed With

photon transfers the momentum ∆ p = h · ν/c 2π
onto the Na-atom and decreases its velocity by k= = 0.94 ×107 m−1 ,
λ
∆v = ∆ p/m = h · ν/(m · c) ≈ 3 cm/s. 1
The velocity decreases per s is then a = 3 · 1.6 × γ = = 6 ×107 s−1 ,
τ
107 = 4.8 ×107 cm/s2 = 4.8 ×105 m/s2 . In order to R0 = 106 s−1 and δ = 2π · 107 s−1 ,
bring the Na atom to rest, N = 700/0.03 = 23,333
absorptions are necessary. This takes a time pm ≈ µB = 9.28 ×10−24 J/T ,
b = 10−2 T/m
23,333
T= ≈ 1.5 ×10−3 s = 1.5 ms .
1.6 ×107 we obtain
The deceleration path length is D = 106 · 9.28 ×10−24 · 10−2
1 16 · 0.94 ×107 · 2π · 107
∆z = v0 T − aT 2 × 2 N/m
2 36 ×1014 1 + 16π 2 /36
= 1.5 ×10−3
= 3.7 ×10−2 N/m .
1
× 700 − · 4.8 ×105 · 1.5 ×10−3 m
2 The oscillation frequency is:
−3
= 1.5 ×10 (700 − 360) m
Ω = D/M
= 0.51 m .
= 3.7 ×10−2 /(23 · 1.66 ×10−24 ) s−1
2. The net force on the atoms is = 3 ×1010 s−1 .
F = −a · v with The damping constant is
16δk2 a
a= * +2 . β= = 2.1 ×103 s−1
γ 2 1 + (2δ/γ)2 M
⇒ τdamp = 480 µs .
With δ = 2π × 107 s−1 , k = 2π 7 −1
λ = 0.94 ×10 m ,
γ = τ1 ≈ 6 ×107 s−1 , R0 = 106 The atoms perform 3 ×1010 · 4.8 ×10−4 = 1.4 ×107
oscillations, before the oscillation amplitude has
⇒ a decreased to 1/ e of its initial value.
16 · 2π · 107 · 1.06 ×10−34 · 0.942 · 1014 · 106 4. The mean distance d is related to the density N by
= √
4π 2 · 1014 [1 + (4π/6)2 ]2 d = N −1/3 ⇒ d = 10−13 cm
3
−7
15 ×10 = 0.46 ×10−4 cm = 4.6 ×10−7 m .
= = 8.2 ×10−23 N s/m .
182 ×1014
8.2 ×10−23 The de Broglie wavelength is
⇒ a/M = = 2.1 ×103 s−1
23 × 1.66 ×10−24 h
M λdB = √ = d = 4.6 ×10−7 m
⇒ τdamp = = 0.48 ×10−3 s = 480 µs . 3mkB Tc
a h
⇒ Tc = 2
3. The restoring force in z-direction is 3mkB d
Fz = −D · z , 6.6 ×10−34
=
3 · 23 × 1.66 ×10 · 1.38 ×10−23· 6.72× 10−14
−27
where the force constant is = 9.3 ×10−7 K = 930 nK .
16kδ
D = R0 · pm · b · 2 . BEC occurs under these conditions at Tc = 930 nK.
γ2 1 + 4δ2 /γ 2 The atoms in the trap can reach a region, where the
magnetic field energy E M = −µm · B equals their For v = 20 this gives with ωe = 30 cm−1 , ωe xe =
kinetic energy E kin = 12 mv2 with v2 = 3kT
m . 0.04 cm−1
3 3 1
⇒ E kin = kT = · 1.38 ×10−23 · 9.3 ×10−7 J . ∆E = hc [2ωe − 82ωe xe ]
2 2 2
The magnetic field is = 5.61 ×10−22 J = 3.5 ×10−3 eV .
B Em 3
kT The laser pulse can therefore excite
B = b·r ⇒ r = = = 2 . 0.09
b µm · b µm · b n= = 26
0.0035
With µm Na 2S1/2 ≈ µB = 9.27 ×10−24 J T−1
vibrational levels of the Cs2 -molecule.
1.5 × 1.38 ×10−23 · 9.3 ×10−7 6. The intensity at the output of the Michelson
⇒ r= m
9.27 ×10−24 · 10−3 interferometer is:
= 2.08 ×10−3 m = 2.08 mm . I0
It = · cos2 (∆ϕ/2) ,
2
With a density of 1013 cm−3 there are N = 1013 ·
where ∆ϕ = 2π · ∆s/λ is the phase difference bet-
3 πr = 3700 atoms in the trap.
4 3
ween the two interfering beams. If ∆s changes by
5. The energy of a vibrational level with quantum
δ ⇒ ∆ϕ changes by δϕ = 2πδ/λ. The intensity
number v is:
change
!
1 1 2 ∆ϕ + δϕ ∆ϕ
E(v) = hc ωe v + − ωe xe v + . It − It ≤ 10−8 I0
2 2 2 2
should be smaller than 10−8 I0 . With ∆ϕ = π ⇒
The energy width of the femtosecond pulse with
Gaussian time profile, for which ∆ν · ∆T = 0.44 is ∆ϕ + δϕ ∆ϕ δϕ
cos = cos cos
2 2 2
∆E = h · ∆v = 0.44h/∆T . ∆ϕ
− sin sin(δϕ/2)
2
With ∆T = 2 ×10−14 s ⇒ ∆E = 1.5 ×10−20 J = = − sin(δϕ/2) ≈ −δϕ/2
0.09 eV. The energy separation of the vibrational
I0
levels is ⇒ It = · δϕ ⇒ δϕ ≤ 4 ×10−8 rad .
4
1 The phase of a plane wave is sensitive to the position
∆E = (E(v + 1) − E(v − 1))
2 of the plane mirror surface, averaged over the whole
1 surface. Deviations from an ideal plane, caused by
= hc [2ωe − (4v + 2)ωe xe ] .
2 the atomic structure, are averaged out.
References
Textbooks on Atomic Physics Chapter 1

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Subject Index
a–b-diagram 59 – MO 329 autoionization 228, 276, 367

absolute mass 51 – MO-LCAO 332 Autrecourt, N. 8
absorption – self-consistent field 219 average number of photons per mode
– continuous 273 Argon laser 305 243
– Doppler-free two-photon 182 Aristoteles 8 Avogadro, A. 11
– effective coefficient 275 asymptotic solution 160 Avogadro constant 12, 14, 17
– losses 284 atom
– minimum coefficient 410 – alkali 214 B2 molecule 338
– nonlinear 443 – anti-hydrogen 235 Balmer’s formula 114
– relative 428 – carbon 224 Balmer series 170
– spectrum 110 – doubly excited 276 band 364
absorption coefficient 267 – exotic 233 – fundamental 394
absorption edges 270 – helium 197 – head 365
abundance – images 19 – origin 362
– isotopic 62 – interferometry 481 – parallel 395
actinides 212 – kaonic 235 – perpendicular 395
Airy formulas 419 – laser 480 – system 364
α-decay 135 – multielectron 217 – vibrational 362
amplifier – myonic 233 beam
– optical 300 – pionic 235 – atomic 42
amplitude – quantum structure 109 – molecular 441
– quadrature 489 – stability 115 beam profile for the fundamental
angular momentum 150 – thermal He 99 modes 294
– conservation 249 – tin 224 BEC 479
– coupling 220 atomic beam 42 Beer 443
– electronic 335 atomic clock 487 Beer’s law 443
– operator 150 atomic force microscope 26 bending vibration 391
– quantum number 151 atomic interference pattern 97 benzene 383
– rotational 350 atomic mass unit (AMU) 10 Bernoulli, D. 9
– vibrational 391 atomic orbital 328 beryllium 207
anti-proton 236 – 1s deformation 332 Berzelius, J.J. 10
anti-Stokes radiation 448 – deformation 328 binding
apodization 430 atomic polarizability 346 – covalent 348
approximation atomic spectrum 109 – ionic 348
– adiabatic 349 atomic unit 328 – types 348
– Born–Oppenheimer 367 atomic weight 10 binding energy 329, 332, 355
– breakdown of the attenuation coefficient 267 Biot–Savart’s law 175
Born–Oppenheimer 392 Auger blue-shadowed 365
– Heitler–London 330 – effect 229 Bohr’s atomic model 112
– LCAO 325 – process 229 Bohr magneton 166
564 Subject Index
Bohr radius 113, 160 – charge exchange 38 – integral 63, 67

bolometer 423 – cross section 28, 409 – integral scattering 62
Boltzmann, L. 8 – elastic 262 – threefold differential 454
Boltzmann distribution 243 – inelastic 262 crystal
bond – phase-changing 263 – birefringent 303
– chemical 341, 373 – quenching 466 – body-centered cubic 30
– covalent 342 – radius 261 – face-centered cubic 30
– homopolar 342 – reactive 409, 466 – liquid 484
bonding – time 261 – uniaxial birefringent 308
– hydrogen 348 – uenching 262 cyclotron frequency 60
– localized 384 collision broadened emission line
– localized σ-type 383 261 Dalton, J. 9, 10
Born’s statistical interpretation 121 collision complex 402 damping constant 256, 478
boron 207 collision-induced rate 254 De Broglie wavelength 95
Bose–Einstein condensation 479 colour-center laser 299 deflection angle 70
boson 201 Compton effect 89, 268 degenerate 142, 162
boundary conditions 131 Compton wavelength 90 delocalized 383
bound-bound transition 275 concept of nature 122 – π orbitals 384
Bragg diffraction 273 condition Democritus 7, 8
Bragg reflection 97 – phase-matching 449 density
bremsstrahlung 264, 274 configuration – effective 426
Brownian motion 20 – electron 220 – energy 79
– interaction 219 – mode 82
carbon 207 – two-electron 226 – momentum 80
CARS 449 contribution – packing 30
cathode rays 32 – monopole 343 – population 387
CCD array 412 conversion efficiencies 309 – power 81
center of mass 157 coordinate – probability 103, 118
centrifugal distortion 352 – elliptical 322 derivative
chaotic movement 118 – inversion 334 – first 427
charge distribution 68 – mass-weighted 389 detector 421
chemical laser 305 Coriolis force 392 – Langmuir–Taylor 466
clamped nuclei 330 correlation diagrams 340 – phase-sensitive 433
classical particle paths 118 correspondence principle 190 – thermal 422
classical wave description 93 Coulomb force 32 – time constant 423
Clausius, R.J. 8, 9 Coulomb-repulsion 330 determinant
cloud chamber 23 coupling – Slater 219
cluster 396 – between vibrations and rotations device
– mass distribution 399 392 – photoconductive 423
– melting temperature 400 – fine structure energies 221 – photovoltaic 423
– size 398 – intermediate cases 224 diagram
– temperature 400 – j– j 223 – Slater 226
CO2 -laser 306 – L–S 220 – Walsh 379
CO2 molecule 378 – of angular momenta 220 diatomic molecules
coherence length 298 – schemes 220 – vibrations 354
coherent control 484 – spin-orbit 203, 336 difference-frequency generation 310
coincidence experiments 454 – terms 391 diffraction
CO-laser 305 – vector diagram 223 – atoms 96
collision covalent binding 348 – Bragg 273
– broadening 260 cross section – electron 95, 106
– central 66 – differential 62, 63, 67, 72 – losses 284, 290, 294
Subject Index 565
– X-ray 14 – mass 39 equation

diffusion 29 – mechanical model 192 – uncoupled 390
– coefficient 14 – motion 353 equilibrium distances 351
– process 22 – multiplier 37 Erbium laser 299
dipole – optics 45 excess 420
– approximation 245 – Rydberg 231 excimer 306, 340
– electric 343 – shell 205 excitation
– Hertzian 244 – spin 200 – inner-shell 229
dipole moment electronic transition 362 – one-electron 227
– induced 344 electron microscope 24, 50, 99 – simultaneous 228
– momentary 345 electron model 191 – single electron 227
– total 393 electron radius exotic atom 233
Dirac equation 157, 185 – classical 191 expansion
discharge electron shell 165 – adiabatic 398
– hollow cathode 435 electron spin 172 – Dunham 357
dispersion 100 element expansion of the universe 42
– angular 412 – alkali 212 expectation value 147, 164
– linear 412 – alkaline earth 212 – for the location x 147
– of FPI 421 – chemical properties 213 – of the kinetic energy 148
– of the wave packet 107 – piezo 26 experiment
displacement – trans-uranium 212 – ideal 465
– mass weighted 390 elliptical coordinate 322
dissociation energy 355 elliptical mirror arrangement 439 Fabry–Perot-etalon 304
distribution emission factor
– angular 454 – coefficient 35 – Hönl–London 393, 395
– function 21 – field 35 fadenstrahlrohr 40
– Gaussian 70 – induced 242 Fano
– radial of atomic electrons 205 – secondary electron 36 – profile 277
– temperature 450 – spectrum 110 Fano parameter 277
Doppler broadening 258 – spontaneous 242 Fano profile 276
Dunham coefficients 357 – thermal 35 Fano-profile 367
duo-plasmatron 39 Empedocles 7 Faraday’s law 14
energetic order Faraday polarization rotator 304
eigenfunction 148 – of the orbitals 337 femtosecond 310
– common 153 energy Fermi-contact interaction 182
eigenvalue 148 – binding 329 fermion 201
eigenvolume 28 – density 79 field
Einstein coefficient 242 – dissociation 355 – axially symmetric 45
– for absorption 242 – equipotential curves 405 field ionisation 135
Einstein–de Haas effect 173 – fine structure coupling 221 finesse 421
Einstein–Podolski–Rosen paradox – ionization 114, 208, 400 fine structure 174
497 – mean rotational 356 – component 175, 337
electric field – of Rydberg levels 232 – constant 177
– perpendicular 44 – rotational 354 – coupling energies 221
electric quadrupole moment 252 – surface 373 – labeling of component 221
electron 33 – transfer 285 – Sommerfeld’s constant 176
– configuration 220, 337 – zero-point 137 – splittings 336
– delocalized 382 energy density fine-structure component 271
– diffraction 95, 106 – spectral 243 fingerprint region 428
– free 34 energy pump 283 flashlamp
– independent 199, 217 Epicurus 8 – helical 287
566 Subject Index
floating ball 43 gain factor 284 – sp2 376

fluctuation gas – sp3 376
– of the laser frequency 296 – discharges 32 hydrogen atom 161
– phase 297 – effusion 42 hyperfine component 181
– technical 297 gas constant 12 hyperfine constant 181
fluorescence 253 gas laser 304 hyperfine structure 180, 443
– laser-induced 438 gate function 430
focal length Gay-Lussac, J.L. 11 imaging
– of a magnetic lens 49 Gedanken-experiment 120 – of electron beams 45
– of a magnetic sector field 50 generator impact parameter 64, 74
focusing – photocurrent 424 induced dipole moment 344
– double 55 gerade 334 induced emission 242
– velocity-independent 53 giant pulse 311 infrared-active 394, 449
force globar 428 inner-shell excitation 229
– Coriolis 392 Gordon 283 integral
– Coulomb 32 grating – overlap 377
– nuclear 73 – concave 416 intensity 80, 92
– restoring 389 – equation 415 – of a rotational line 387
formaldehyde molecule 381 – Rowland 452 – spectral 80
formula grating equation 272 intensity distribution of the
– modified Rydberg 216 grating pair 316 fundamental modes 293
– Rydberg 230 gravitational redshift 92 interaction
– Schawlow–Townes 297 greenhouse effect 360 – configuration 219
Fortrat-diagram 362, 364 ground state – dipole–dipole 182
Fourier limitation 303 – helium 202 – exchange 342
Fourier transformation 429 – of the H atom 170 – Fermi-contact 182
Franck–Condon factor 363 gyromagnetic ratio 173 – multipole 342
Franck–Condon principle 366 – octupole 346
Franck–Hertz experiment 115 H2 molecule 329 – rotation-vibration 355
free-electron laser 299 H2 AB molecule 381 – van der Waals 345
free spectral range 419 H2 O molecule 373 – virtual 185
frequency halogens 213 interference
– cyclotron 60 hard spheres 17, 67 – effects 464
– modulation 426 Hartree–Fock method 219 – fractional order 420
– tunnel 381 Hartree method 218 – multiple-beam 418
frequency selective optical He2 molecule 338 interference pattern 94
elements 295 He2+
2 338 interference phenomena 119
frequency spectrum heat interferometer
– of optical resonators 294 – conduction 29 – Fabry–Perot 419
frequency spectrum of induced – specific 12 – Mach–Zehnder 16
emission 288 Heisenberg’s uncertainty principle – Michelson 417, 428
Fresnel number 291 104 interferometry
full-width at half-maximum He–Ne laser 287 – atom 481
255 Heraclitus 8 – neutron 98
function Hermitian polynomials 139 – X-ray 16
– amplitude 297 hidden parameter 497 inversion 284
– deflection 464 Holmium laser 299 inversion tunneling 136
– hyperbolic 402 Hönl–London factor 363 ion 31
– partition 388 Humboldt, A.v. 11 – free 37
– spherical harmonic 145 hybridization 374 – H+2 321
– symmetric spin 200 – sp 375 – optics 43
Subject Index 567
– sources 38 – neodyniumm-glass- 299 magic numbers 399

– trapped 487 – pulsed 285 magnetic moment
ionic contribution 332 – Q-switched 310 – nuclear 181
ionization – ruby flashlamp-pumped 286 magnetization 173
– electron impact 37 – semiconductor 300 magnetron
– energy 114 – single mode 295 – motion 61
– field 230 – solid-state 299 – movement 61
– thermal 38 – three level 287 Maiman 283, 287
ion multiplier 440 – Titan-Sapphire 299, 314 maser 381
ionosphere 38 – tunable diode 433 mass
isomers 380 – ultrashort pulses 410 – absolute 51
isotope 61 lattice constant 15 – photon 92
isotopic abundance 62 LCAO – relative atomic 51
– improvements 327 mass absorption coefficient 269
jellium model 399 learning algorithm 485 mass spectrometer 51
Legendre’s polynomials 145 – quadrupole 58
kanalstrahlen 32 Lenard–Jones potential 31, 262, – time-of-flight 55
Kerr lens 314 346, 464 mass spectrum 56
– mode-locking 313 lens – Nan 58
kinetic gas theory 17 – converging 45 Mathieu’s differential equations 59
Kirchhoff’s diffraction theory 292 – electro-optic 45 matrix elements 244, 359
Kirchhoff’s law 81 – magnetic 48 matter wave 100
Kolos 333 leucht-electron 214, 241 – function 101
K-shell 205 Leucippus 7 Maxwell, J.C. 8, 9
level Maxwell–Boltzmann distribution
Lamb, Willis 444 – vibronic 300, 396 258
Lamb dip 444 Li2 molecule 338 mean free path length 28, 63
Lamb shift 185 lifetime 228 mean quadratic deviation 148
Landé factor 174, 178 – effective 254 measuring process 121
lanthanides 212, 213 – mean 253, 401 medium
Laplace operator 128 light – active 283
laser – circular polarized 248 mercury lamp 244
– argon 304, 305 line method
– atom 480 – kernel 255 – ab-initio 218
– chemical 305 – profile 255 – Hartree 218
– CO 305 – wings 255 – Hartree–Fock 219
– CO2 306 linewidth metrology
– color-center 299, 300 – natural 256, 257 – optical 485
– diode 300 liquid crystal 484 microscope
– dye 301 LISA 494 – atomic force 26
– erbium- 299 lithium 206 – electron 24, 50, 99
– excimer 306 Littrow-grating 306 – scanning electron 25
– fixed-frequency 298 localization of the particle 104 – transmission electron 24
– flashlamp-pumped dye 302 lone pairs 378 – tunneling 26
– free-electron 299 Lorentzian profile 257 microwave range 352
– gas 304 Lorentz transformation 175 mode 82
– He–Ne 287 L-shell 205 – density 82
– Holmium 299 Lyman α-line 259 – fundamental 292
– line width 297 – of open resonator 291
– mode-locking 311 Mach, Ernst 7 – phase-coupled 312
– neodymium 299 macroscopic measurements 410 – spectral density 83
568 Subject Index
– TEM 292 Na D-line 259 – microwave 425

– transverse 293 neodynium-glass-laser 299 Ostwald, W. 7
model neutron 62 overlap integral 325
– jellium 399 – interferometry 98 overtone-transitions 361
– semiclassical 114 – spectrometer 98
– shell-structure 399 NH3 molecule 380 P-transition 362
modified Rydberg formula noise equivalent input power NEP pair formation 268
216 421 para-helium 204
modulation noncrossing rule 341 parity 250
– frequency 426 nonlinear absorption 443 Parmenides 8
– phase 433 nonlinear optic 307 particle
modulator normalization constant 332 – free 128, 129
– electro-optic 433 normal vibration 388, 390 – in a box 136
mole 12 nuclear force 73 particle aspects of light 92
– volume 12 nuclear g-factor 181 particle model 79
molecular beam 441 nuclear magneton 181 particle wave 99
molecular dynamics 405 partition function 84
molecular polarizability 461 observable 148 Paschen–Back effect 184
molecule 11 octupole interaction 346 path
– acetylene 375 oil droplet 33 – elliptical 165
– aromatic 382 one-dimensional box Pauli principle 201
– asymmetric rotor 388 – energy 137 penetration depth 131
– B2 338 operator 147, 148 periodic system 211
– butadiene 382 – commutable 149 Perrin, J.B. 13
– CO2 378 – Hermitian 149 perturbations 409
– diatomic 321 – of the angular momentum 150 phase grating 97
– formaldehyde 381 – reflection 334 phase matching 308
– H2 AB 381 optic – angle 309
– H2 329 – electron 45 phase velocity 100
– H2 O 373 – nonlinear 307 photo-association 481
– He2 338 optical amplifier 300 photodiode 423
– Li2 338 optical fiber bundle 439 photodissociation 483
– NH3 380 optical frequency mixing 309 photoeffect 35, 268
– polyatomic 373 optical pulse photoelectric effect 87
– rigid H+2 322 – compression 314 photoionization 37, 274
– symmetric top 386 – ultrashort 316 photomultiplier 424
moment optical reflection coefficient 133 photon 84, 91
– of inertia 384 optical trapping 477 – mass 92
– principal 385 orbital – spin 91
– quadrupole 343 – antibonding 337 photon avalanche 285
Morse, P.M. 347 – bonding 337 photon number per mode 289
Morse potential 347, 356 – hybrid 374 photon recoil 187, 473
MOT 477 – molecular 323, 325 photosphere 38
M-shell 205 – sp-hybrid 375 π-meson 235
multielectron atom 217 orbital angular momentum 159 Planck’s constant 84
multiplet 220 orbital magnetic moment 166 Planck’s formula 243
– structure 222 order Planck’s radiation law 82, 84
multiplicity 202, 227, 336 – energetic 333 planetary atom 232
multipole interaction 342 ortho-helium 204 planetary model 112
multipole transition 251 oscillator plasma 38
myonium 237, 238 – harmonic 139, 354 plasma-frequency 68
Subject Index 569
Plato 8 – Gaussian line 260 – resonance 448

Pockels cell 311 – line 263 Ramsauer effect 139
pointing vector 80 – Lorentzian 257 random walk 70
point-like charge 192 – spectral 256 rate constant 401
Poisson distribution 93 – Voigt 260 Rayleigh 411
polarizability property Rayleigh–Jeans radiation law 83
– atomic 346 – optical 400 reaction
– molecular 461 – symmetry 334 – absolute rates 404
polarization proton 62 – chemical 401
– beam splitter 311 Proust, J.L. 9 – constant 401
– dielectric 307 pump and probe experiments 406 – coordinate 403
polarized – endothermic 403
– circularly 91 Q-factor 289 – exchange 404
– linearly 91 Q-line 362 – exothermic 403
population inversion 286 quality factor 289 – first order 401
positronium 237 quantization axis 153, 184 – inverse 403
potential quantum bits 498 – order 401
– barrier 381 quantum defect 216 – rate 401
– difference 366 quantum electrodynamics 122, 157 – second order 401
– effective 217 quantum nondemolishing experiment recombination
– interaction 262 122 – radiation 277
– Lenard–Jones 31, 262, 346, 464 quantum number 161, 324 – radiative 277
– monotonic 66 – angular momentum 151 – rate 277
– Morse 347, 356 – magnetic 151, 248, 249 – three-body 277
– parabolic 347 – projection 335 – two-body 277
– spherically symmetric 143 – spin 250 red-shadowed 365
– van der Waals 344 – spin projection 324 reduced mass 351
potential barrier 130 quantum structure of atoms 109 reflection
potential curves 326 quark 181 – Bragg 97
potential energy qubit 498 – losses 284, 290
– curves 323 – loss factor 290
potential step 132 R-transition 362 reflection coefficient 132, 134
potential well 138 radiation reflector
power – anti-Stokes 448 – cylindrical 287
– resolving 430 – blackbody 80 reflectron 58
– spectral resolving 411, 430 – cavity 81 refractive index 313
predissociation 358 – power 257 relative absorption 428
pressure broadening 262 – recombination 277 relative atomic mass 51
principle – spectral 81 relative motion 157
– building-up 205 – Stokes 448 – of electron and nucleus 159
– Pauli 201 – synchrotron 451 relativistic correction 170
probability – thermal 243 relativistic energy shift 171
– density 103, 118 radiation field relativistic mass correction 171
process – isotropic 247 repulsive potential 326
– diffusion 22 radiative recombination 274 resolving power 430
– electrolytic 14 radical resonator
– photographic 400 – NH2 379 – enhancement 309
– visual 451 raisin cake model 68 – open optical 290
product-ansatz 159 Raman, Chandrasekhara 447 – optical 283, 289
profile Raman active 449 restoring force 389
– Fano 276 Raman effect ring-resonator 303
570 Subject Index
rotation 384 single mode laser 295 – of our sun 278

rotational barrier 357 size – photoelectron 455
rotational constants 353 – cluster 399 spin
rotational energy 354 Slater determinant 330 – absolute value 173
rotational term values 351 Slater orbitals 333 – electron 200
rotation-vibration interaction 355 solar constant 85 – magnetic moment 173
rotor spatial distribution spin-orbit coupling 174
– asymmetric 385, 388 – of the electron 163 – constant 176
– rigid 350 spatial resolution 107 splitting
– symmetric 385 spectral gain profile 295 – inversion 381
– vibrating 355 spectral intensity 80 squeezing 489
Rowland arrangement 168 spectral radiation 81 stable solutions 59
Rutherford spectral resolving power 411, 430 star
– atomic model 70 spectral response 421 – binary 493
– scattering formula 71 spectrograph Stark-effect
Rydberg atom – parabola 51 – linear 460
– doubly excited 367 spectrometer 411 – quadratic 461
Rydberg constant 113, 190 – grating 414 Stark shift 427
Rydberg formula 230 – infrared 428 Stark-spectroscopy 459
Rydberg state 229, 231 – ion-cyclotron-resonance 60 state
– neutron 98 – doubly excited atomic 228
scattering – prism 413 – electronic 333, 334
– classical 64 spectroscopy – entangled 497
– electron 453 – cavity-ringdown 436 – excited atomic 227
– inelastic 465 – electron 453, 456 – excited molecular 338
– losses 284 – excitation 438 – metastable 228
– plane 64 – Fourier transform 428 – metastable excited 258
– potential 64 – infrared 428 – metastable He 288
– rainbow 464 – ionization 439 – Rydberg 229, 231
– reactive 466 – Lamb dip 444 – singlet 201
– super-elastic 448 – laser-absorption 432 – triplet 201
scattering coefficient 267 – microwave 425 statistical interpretation 103
scattering experiment 68 – nonlinear laser 443 statistical weight 243, 410
Schawlow, A.L. 283, 381 – optoacoustic 434 Stefan–Boltzmann’s law 86
Schawlow–Townes formula 297 – optogalvanic 435 Stefan–Boltzmann constant 86
Schrödinger’s cat 498 – photoacoustic 435 stellar atmospheres 260
Schrödinger equation 127 – photoelectron 455 Stern–Gerlach experiment 171
– time-dependent 128 – Raman 447 Stern–Vollmer plot 254
secondary emission coefficient 36 – saturation 444 Stokes’ law 34
second harmonic 308 – time-resolved 482 Stokes radiation 448
selection rule 241, 247 – two-photon 446 storage ring DORIS 451
– for harmonic oscillator 361 – ZEKE 457 structure
– parity 249 spectrum – bipyramidal 377
semiclassical model 114 – absorption 110 – rotational 395
sensitivity 410 – atomic 109 subshell 206
– absolute 421 – continuous 273, 367 sum frequency 310
shell-structure model 399 – continuous emission 278 supra-liquid 480
shielding constant 198, 211 – emission 110 surface
short laser pulses 310 – helium 204 – equipotential 46
signal-to-noise ratio 411 – iron 224 susceptibility
silver halide grains 400 – of CO 427 – electric 307
Subject Index 571
symmetric top 354 – electronic 362 vibration period 141

– molecules 386 – forbidden 245 virtual interaction 185
– near 388 – fundamental 361 viscosity
– oblate 386, 387 – magnetic dipole 251, 252 – of a gas 29
– prolate 386, 387 – matrix elements 358 Voigt profile 260, 442
symmetry – multipole 251 volume
– axis 384 – overtone 394 – atomic 208
– group 380 – probability 241, 244
– operations 380 – quadrupole 251 wave
– selection rules 396 – radiationless 466 – gravitational 493
system – radiative 466 wave description 79
– four-level 288 – spontaneous 242 wave equation 128
– π-electron 382 – state dynamics 483 wavefunction 161
– two-level 287 – two-photon 182, 253 – normalized 162
– vibrational-rotational 360 – of the harmonic oscillator 140
technique transport – parity 334
– Doppler-free 441 – coefficients 28 wavelength-tunable light source 298
temperature trap wave packet 100, 405, 482
– absolute 19 – magneto-optical 477 – dispersion 107
term assignment 184 tunnel effect 133, 358 – spread of the 130
term values 337 two-dimensional box 142 – width 106
theory which way experiment 495
– nonlocal 497 ultrashort optical pulse 316 Wien’s law 86
theory of the photo effect 88 ultraviolet catastrophe 83 Wigner, Eugene 341
thermal dissociation uncertainty relation for energy and work-function 35, 87
– of H2 168 time 108
thermopile 423 ungerade 334 X-ray 263
Thomas factor 175 – characteristic 264
Thomson’s atomic model 68 vacuum ultraviolet 168 – characteristic fluorescence 265
threshold condition 284 valence method 329 – diffraction 14
Titan-Sapphire laser 314 van der Waals constant 346 – fluorescence 271
Titan-Sapphire-laser 299 van der Waals equation 28 – scattering 266
TOF 55 van der Waals interaction 345 – total reflection 272
– broadening 473 van der Waals potential 344 – wavelength 271
– design 58 velocity 231
total dipole moment 393 – group 101 YAG 299
Townes, C.H. 283, 381 velocity selector 463 Young’s double slit experiment 119
transformation vibration
– Hadamar 498 – asymmetric stretch 391 Zeeman component 166, 249
transition – bending 391 Zeeman effect 166
– bound-bound 275 – normal 388, 390 – anomalous 177
– combination 394 – symmetric stretch 391 Zeeman splitting 167
– dipole moment 245 vibrational constants 354 Zeiger 283

Chronological Table of Atomic and Molecular Physics Development

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Chronological Table of Atomic and Molecular Physics Development

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Chronological Table

for the Development of Atomic and Molecular Physics

developed by C. Cohen-Tannoudji and cowor- 1998 First demonstration of a continuous coherent

pVM pM When a colloid molecule has an average mass num-

The radius r0 of the spheres is (according to

2d sin ϑ = mλ The ratio pi = a/VM2 is called the “internal pressu-

Fig. S.3. With an acceleration voltage U the velocity vz is

The fraction of atoms scattered into the angular ϑ2

For the Thomson model we obtain for a me-

value dν. The maximum of Sν∗ at νm is not at νm = c/λm !

∆E r (n = 1, Z = 79) = 5.6 eV . 9. At room temperature (T = 300 K) only the ground

11. For the uncertainty ∆r = a the kinetic energy of g(t) = g0 e−i(E/ )t

For a potential well with depth E 0 the potential

For E 0 = ∞ ⇒ α = ∞ and the arccotg becomes ∂ϑ zy/r 2

9. For E = 12 E 0 we obtain from (4.26a): Inserting the numerical values

∆ν = δν/F ∗ . For the isotope T = 31 H it is

With R = 0.95 ⇒ F ∗ = 61 and µ = m e · 0.999818 .

1.5 ×1010 The wavenumber and frequency of the Lyman α-

The hyperﬁne-splittings are: dτ = r12 dr1 sin ϑ dϑ dϕ

with Z = 2 for the He atom.

The integral can be solved analytically

E = −1.30 ×10−17 J = −82 eV . 6788 2

E kin (e− ) = 0 ⇒ −E n = hν . The time dependent ﬂuorescence power can be

The emitted energy is related to the power by

∆s = v ∆T = 6.9 ×102 × 5.3 ×10−5 m ν1 − ν0 = 0.1 δνD = 6.77 ×108 s−1

3. a) The frequency separation of the transmission we obtain

The solution of the homogeneous equation (B = 0) e2

The equation for the electrons

8. The vibrational frequency for the model of

Fr = −1.3 ×10−8 N. For the bending vibration ν2

This should be compared with the average distance Chapter 11

For our example of the HCl-molecule is Jk = 1, 3. The grating equation is

For T = 300 K the absorption coefﬁcient becomes The angular difference is

α = 2.1 ×10−4 m−1 . ∆β = 0.04◦ = 7.36 ×10−4 rad .

1/(2τ) = 109 /64 ≈ 1.6 ×107 s−1 . Each absorbed With

Textbooks on Atomic Physics Chapter 1

a–b-diagram 59 – MO 329 autoionization 228, 276, 367

Bohr radius 113, 160 – charge exchange 38 – integral 63, 67

– X-ray 14 – mass 39 equation

ﬂoating ball 43 gain factor 284 – sp2 376

– sources 38 – neodyniumm-glass- 299 magic numbers 399

– TEM 292 Na D-line 259 – microwave 425

Plato 8 – Gaussian line 260 – resonance 448

rotation 384 single mode laser 295 – of our sun 278

symmetric top 354 – electronic 362 vibration period 141

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