Abstract
Schrödinger’s equation3 in c.g.s. units for an electron in the field of a nucleus of charge Ze and of infinite mass is
and in Hartree’s atomic units (see Introductory Remarks) is
An erratum to this chapter is available at http://dx.doi.org/10.1007/978-3-662-12869-5_6
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References
J. W. DuMoxn and E. R. COHEN: In this volume and private communication.
Numerical values, found in older theoretical references (including ref. [10] of our bibliography), which are based on the atomic constants, should be treated with great caution: The older values of some atomic constants were in error by much more than the statistical errors in the older experiments (due to systematic errors not expected at the time).
We shall use throughout the symbol d for the LAPLACE operator (axz -}- ayz -~- ôz2), instead of the symbol V2 which is more commonly used in English and American texts.
x, and y are measured in atomic units.
Cf. Theory of the ZEEMAN effect, Sect. 45.
Compare, for example, ref. 171, A. SOMMERFELD, Wellenmechanischer Ergänzungsband, p. 70 and the original work of E. SCHRÖDINGER, Abhandlungen zur Wellenmechanik, p. 1.
The alkali atoms which are more closely related to hydrogen than any other atoms do not show this degeneracy. To be sure, the discrete energy levels of the alkali atoms can be calculated to a good approximation by considering only the motion of the valence electron in the field arising from a charge distribution of closed shells, but this field is a non-Coulomb central field and levels of like n and different l have entirely different energies.
It should be noted that the atomic unit of action is h = h/22r and not h. The frequency of the spectral line may be obtained in c.g.s. units by dividing the energy difference (in c.g.s. units) between the initial and final states by h; or, if the energy difference is expressed in atomic units, by dividing by 27r.
E. R. COHEN: Phys. Rev. 88, 353 (1952).
We shall often use simply the symbol Ry for this quantity although, strictly speaking, we have defined Ry as a frequency, e Roe.
For a list of observed wave numbers of spectral lines in light atoms and ions see: Atomic Energy Levels, Vol. 1, U.S. National Bureau of Standards, Circular 467, 1949.
Cf. W. GORDON: Ann. d. Phys. 2, 1031 (1929).
The numerical factor (2 e)1 is included only for the sake of convenience in later calculations.
For properties of the confluent hypergeometric function see ref. [8], Chap. 16 or the article of J. MEIXNER, Vol. I of this Encyclopedia. We shall in general omit the word “confluent ”. We shall use the more general function F (a, ß, y, x) very rarely and will call it the “general hypergeometric function ”.
Cf. A. SOMMERFELD: Wellenmechanischer Ergänzungsband, p. 292, ref. [7]; see also our Sect. 36e.
Cf. JAHNKE-EMDE: Tables of Functions, especially p. 166 (differential equation), p. 98 (asymptotic formula), p. 90 (series expansion).
See Sect. 53.
The asymptotic formula for the BESSEL function can thus be looked upon as a special case of the WKB procedure.
See, for example, E. SCHRSDINGER, Ann. d. Phys. 80, 131 (1926).
Cf. Sec. 63 and particularly W. GORDON, Ann. d. Phys. 2, 1031 (1929).
See also M. STOBBE: Ann. d. Phys. 7, 661 (1930).
For details, see the work by MOTT and MASSEY, ref. [7] of the bibliography. For tables of COULOMB wave functions see N.B.S. Appl. Math. Circ. No. 17, Vol. 1, Washington, D.C. 1952.
UREY, BRICEWEDDE and MURPHY: Phys. Rev. 40, 1, 464 (1932).
For a detailed analysis see E. R. COHEN, Phys. Rev. 88, 353 (1952).
J. W. DuMoND and E. R. COHEN: Rev. Mod. Phys. 25, 691 (1953). — Cf. the preceding article in this volume.
Cf. J. FISCHER, Ann. d. Phys. 8, 821 (1931) paragraph 1; G. WENTZEL, Z. Physik 58, 348 (1929).
Cf. e. g., G. WENTZEL, Z. Physik 58. 348 (1929), Eq. (22). More precisely, u falls off as 0,2—z2)—g
W. GORDON: Z. Physik 48, 180 (1928), cf. also G. TEMPLE, Proc. Roy. Soc. Lond., Ser. A 121, 673 (1928); A. SOMMERFELD, Ann. d. Phys. 11, 257 (1931), paragraph 6. See also p. 47 of ref. [9]
See also ref. [9], p. 47.
To make the system uk complete, the eigenfunctions of the discrete spectrum must, of course, be included.
G. BREIT and H. A. BETHE: Phys. Rev. 93, 888 (1954).
W. GORDON: Z. Physik 48, 180 (1928).
For a potential falling off more rapidly than r-1 at large distances.
With 61 replaced by — a1, where a1 is defined in (4.10). With this substitution (7.2) and (6.30) are identical except for a change in sign [see normalization of Rw, Eq. (4.19)]. W. GORDON: Z. Physik 48, 180 (1928).
YENNIE, RAVENHALL and WILSON: Phys. Rev. 95, 500 (1954).
See Sect. 9 and 70, also ref. [9], pp. 116–119.
This method has, however, been used to obtain the momentum space wave functions for the discrete spectrum of hydrogen, E. A. HYLLERAAS, Z. Physik 74, 216 (1932).
H. WEYL: Z. Physik 46, 1 (1928). — V. Focx: Z. Physik 98, 145 (1935).
More generally, let f (r) and g(r) be two functions, which are complex conjugates of each other, f* (r) = g (r). If F(p) and G (p) are the FOURIER transforms of f and g, respectively, one finds that F* (p) =G(—p).
N. SVARTHOLM: Thesis, Lund 1%5. — R. MCWEENY and C. A. CouLSON: Proc. Phys. Soc. Lond. A 62, 509 (1949). — M. L:vY: Proc. R.y. Soc. Lond. 204, 145 (1950). — E. E. SALPETER: Phys. Rev. 84, 1226 (1951).
See, for instance, JAHNKE and ENDE, Funktionentafeln, 4th Ed., p. 109. Berlin: Springer 1945.
B. A. LIPPMANN and J. SCHWINGER: Phys. Rev. 79, 469 (1950). — M. L. GOLDBERGER: Phys. Rev. 82, 757; 84, 929 (1951). — E. E. SALPETER: Phys. Rev. 84, 1226 (1951).
Eq. (9.2) has been used recently, however, as the starting point of calculations in meson field theory. See, e.g., G. F. CHEW and F. E. Low, Phys. Rev. 101, 1570 (1956).
Actually, the bound states must be included to complete the set.
For a COULOMB potential, f+ still has a singularity at p =k.
Bethe and Salpeter, Quantum Mechanics. 4
See references at the beginning of Sect. 9.
A necessary, but not sufficient, condition for the validity of BORN approximation is tan Si F.s Si s 1.
See references [1], [2], [3] and [12] of the bibliography.
A detailed discussion of the properties of the DIRAC operators is given by R. H. GooD, Rev. Mod. Phys. 27, 187 (1955).
See ref. [3], [12], and [13] of the bibliography.
See ref. [1], Ch. VI; ref. [5], Ch. III and G. PARE and E. FEExnERG, Quantum Theory of Angular Momentum. Cambridge: Addison-Wesley Co. 1953.
Ref. [1], p. 144 or ref. [5], p. 46.
In older books and in ref. [9] the large components are labelled 3, 4 and the small components 1, 2. In these references the term in the HAMILTOxian which involves p differs from ours by a change in sign.
See ref. [2], Sect. 65.
It should also be remembered that (12.7) only holds for a wave function u, which satisfies the DIRAC equation. Consider, for instance, the expression (al (r) u)A where f (r) is an arbitrary function of position, not involving DIRAC operators. Although a commutes with f, p does not, and a valid approximation for (a f u)A is obtained from (12.7) only if we write f (r) to the left of p.
W. PAULI: Z. Physik 43, 601 (1927).
Regarding this factor of two, see L. H. THOMAS, Nature, Lond. 107, 514 (1926).
Unlike the HAMILTONian in the nonrelativistic SCHRÖDINGER theory, H not only involves the spin operator, but also depends explicitly on the eigenvalue. We shall only consider cases where WI «mc2 and shall not encounter any difficulty from the dependence of Hon W.
The expansion parameter in the PAULI approximation scheme, roughly speaking, is (Vic)2, not Vic.
Bethe and Salpeter, Quantum Mechanics.
The statement that j = l f z is merely a specific case of a more general theorem on the eigenvalues j (j +1) of the square of the sum of two commuting angular momentum operators, ka + kb: If the eigenvalues of kâ, kb are la (la I) and lb (lb + 1), then j = I la — lb I • I la — bbl +1,—, la + lb . j is defined as the positive root of j (j + 1) = const.
We can, of course, find a linear superposition of the two solutions, + and —, for fixed l and m, for which a or b vanishes. Such wave functions are eigenstates of ks and s, but not of the HAMILTOxian (13.2), since the eigenvalues X+ and X_ are different. If a is considered very small, the two eigenvalues of the total HAMILTOxian are approximately the same and such a wave function is “almost a stationary state”.
Ref. [1], p. 151.
Ref. [10], p. 310.
These expressions are taken from W. B. PAYNE, Ph. D. Thesis, Louisiana State University 1955 (unpublished). Payne has also tabulated the radial wave functions for the M and N shells. See also E. H. B.RHOP and H. S. MASSEY, Proc. Roy. Soc. Lond., Ser. A 153, 661 (1935). Graphs of the DIRAC wave functions are given by H. E. WHITE, Phys. Rev. 38, 513 (1931). Expressions for the DIRAC wave functions in terms of generalized LAGUERRE polynomials are given by L. DAVIS, Phys. Rev. 56, 186 (1939).
C. G. DARWIN: Proc. Roy. Soc. Lond., Ser. A 118, 654 (1928).
L. K. ACHESON: Phys. Rev. 82, 488 (1951). — L. R. ELTON: Proc. Phys. Soc. Lond. A 66, 806 (1953). — YENNIE, RAVENHALL and WILSON: Phys. Rev. 95, 500 (1954). See also ref. [9], p. 79.
In this section k is linear momentum, not angular momentum. Phys. Rev. 103, 1601 (1956).
YENNIE, RAVENHALL and WILSON: Phys. Rev. 95, 500 (1954). Bethe and Salpeter, Quantum Mechanics.
For a discussion of double scattering and expressions for the “assymetry factor” see ref. [9], p. 78 and 82.
J. H. BARTLETT and R. E. WATSON: Phys. Rev. 56, 612 (1939). — H. FESHBACH: Pbys. Rev. 84, 1206 (1951); 88, 295 (1953). — G. PARZEN and T. WAINWRIGHT: Phys. Rev. 96, 188 (1954). — J. DOGGETT and L. SPENCER: Phys. Rev. 103, 1597 (1956). — N. SHERMAN:
Such an expression was first derived by N. F. MOTT, Proc. Roy. Soc. Lond., Ser. A 124, 425 (1929) but his term in Za was incorrect. The expression quoted in ref. [9] is also wrong. The correct expression was obtained by W. A. MCKINLEY and H. FESHBACH, Phys. Rev. 74, 1759 (1948).
R. H. DALITZ: Proc. Roy. Soc. Lond., Ser. A 206, 509 (1951).
P. A. M. DIRAC: Proc. Roy. Soc. Lond., Ser. A 133, 80 (1931).
In fact, these corrections can be calculated in a consistent manner only according to hole theory.
A. Rusi Nowi Tz: Phys. Rev. 73, 1330 (1948).
M. LEvv: Proc. Roy. Soc. Lond., Ser. A 204, 145 (1950).
We shall simply write 6 for 6P.
H. A. BETHE: Z. Naturforsch. 3a, 470 (1948). — E. E. SALPETER: Phys. Rev. 87, 328 (1952).
Although the operator p • e+e • p is not zero itself, its expectation value with any real and bounded wave function u is — i f dr div (eu2) = 0. It then also follows that the expectation value of 2e • p equals that of e • p — p • e = i div ~.
In carrying out the FOURIER transforms it is useful to write e= - grad 9 _ — i (p — 9’ p) and = curl A = i (p X A +A x p). Note also that, for time-independent potentials satisfying the LORENTZ gauge condition, div A (r) = kA (k) = o.
For a historical survey see ref. PO], p. 317, and A. SOMMERFELD, Naturwiss. 28, 417 (1940) .
Except that there is no splitting for n 1 (j = z only). Nevertheless the energy shift W1 is larger for n = 1 than for any other level.
See ref. [10], p. 319 and W. E. LAMB, Rep. Progr. Physics 14, 19 (1951).
For details on this voluminous subject see ref. [5] or A. SOMMERFELD, Atombau and Spektrallinien, 5th Ed.; or ref. [4], Ch. 6; or Vol. XXXVI of this Encyclopedia.
D. R. HARTREE: Proc. Cambridge Phil. Soc. 24, 111 (1928).
BETHE and SALPETER: Quantum Mechanics of One-and Two-Electron Systems. Sect. 17.
E. FERMI: Z. Physik 48, 73 (1928). — L. H. THOMAS: Proc. Cambridge Phil. Soc. 23, 542 (1927). See also P. GoMSAs, Statistische Theorie des Atoms, Vienna: Springer 1949. and Vol. XXXVI of this Encyclopedia.
L. PAULING: Proc. Roy. Soc. Lond., Ser. A 114 (1927). — J. C. SLATER: Phys. Rev. 36, 57 (1930).
LANDOLT and BÖRNSTEIN: Zahlenwerte und Funktionen, 6. Ed., Vol. I/1 Berlin: Springer 1950.
R. CHRISTY and J. KELLER: Phys. Rev. 61, 147 (1942).
Small remaining discrepancies, due to the finite nuclear size, are discussed by A. SCHAWLOW and C. TOWNES, Science, Lancaster, Pa. 115, 284 (1952) and Phys. Rev. 100, 1273 (1955).
S. BRENNER and G. E. BROWN: Proc. Roy. Soc. Lond., Ser. A 218, 422 (1953).
For a more detailed comparison of theory with the latest experimental data see D. SAXON Ph. D. Thesis, Univ. of Wisconsin and J. E. MACK, Phys. Rev. 87, 225 (1952).
S. COHEN: Ph. D. Thesis, Cornell 1955.
Recent experimental work by D. SAXON indicates a slightly smaller value for the K — LI difference, which would increase the discrepancy by a few Ry.
For treatments of quantum electrodynamics see, for instance, refs. [3], [6] and [11] to [14] of the bibliography.
R. P. FEYNMAN: Phys. Rev. 76, 749, 769 (1949).
H. A. BETHE: Phys. Rev. 72, 339 (1947). See also our Sect. 19ß.
For a list of the classic papers of these authors on quantum electrodynamics see refs. [6], [12], [13] and [14].
N. KROLL and W. LAMB: Phys. Rev. 75, 388 (1949). — J. FRENCH and V. WEissxoPF: Phys. Rev. 75, 1240 (1949). — J. SCHWINGER: Phys. Rev. 76, 790 (1949). — R. P. FEYNMAN: Phys. Rev. 76, 769 (1949).
The expression (18.1) holds only for a nonrelativistic change in momentum, q2,’ (In c)2, but expressions have been evaluated which hold for all values of qv.
R. KARPLUS and N. KROLL: Phys. Rev. 77, 536 (1950).
F. BLOCH and A. NORDSIECK: Phys. Rev. 52, 54 (1937). — W. PAULI and M. FIERZ: Nuovo Cim. 15, 167 (1938).
J. JAUCH and F. ROHRLICH: Phys. Rev. 98, 181 (1955) and Heiv. phys. Acta 27, 613 (1954). — E. L. LoMON: Nuclear Physics 1, 101 (1956).
In (18.4), for instance, the term in g2 is proportional to the charge distribution producing the field, which is a point charge Ze â() (r) for a COULOMB potential.
R. KARPLUS, A. KLEIN and J. SCHWINGER: Phys. Rev. 86, 288 (1952). — M. BARANGER, H. BETHE and R. FEYNMAN: Phys. Rev. 92, 482 (1953).
E. WICHMAN and N. M. KROLL: Phys. Rev. 101, 843 (1956).
H. A. BETHE: Phys. Rev. 72, 339 (1947).
This follows from (19.7) as a special case. For a free electron, the momentum changes by k upon emission or absorption of a quantum. If retardation is neglected, this means that k is negligible compared with p, and therefore the energy En after emission of the quantum, is the same as that before, E0. Then the second term in (19.7) vanishes, q.e.d.
In the covariant evaluation of JET, great care must be taken that the definition of d is equivalent to that in the nonrelativistic calculation of LE.; see footnote 13 of R. P. FEYNMAN, Phys. Rev. 76, 769 (1949).
E. E. SALPETER: Phys. Rev. 89, 92 (1953).
For P-states a term in (19.16), connected with the electron’s anomalous magnetic moment, is multiplied by (1 — 2m/M); see W. BARKER and F. GLOVER, Phys. Rev. 99, 317 (1955).
E. E. SALPETER: Phys. Rev. 87, 328 (1952). A small term in this paper, called d Ecc should be doubled.
No nuclei are known which have a finite electric dipole moment, see ref. [16], Chap. 2. 2 E. E. SALPETER: Phys. Rev. 89, 92 (1953).
A. SCHAWLOW and C. TOWNES: Science, Lancaster, Pa. 115, 284 (1952) and Phys. Rev. 100, 1273 (1955).
L. L. FOLDY: Phys. Rev. 83, 688 (1951).
BETRE, BROWN and STERN: Phys. Rev. 77, 370 (1950)
W. E. LAMB: Phys. Rev. 85, 259 (1952).
E. DAYHOFF, S. TRIEBWASSER and W. LAMB: Phys. Rev. 89, 106 (1953).
J. DUMOND and E. COHEN: This volume. - J. BEARDEN and J. THOMSEN: Atomic Constants. Baltimore: Johns Hopkins University 1955.
E. E. SALPETER: Phys. Rev. 89, 92 (1953). In this paper the notation used in this section is explained more fully.
J. M. HARRIMAN: Phys. Rev. 101, 594 (1956).
M. BARANGER, H. BETHE and R. FEYNMAN: Phys. Rev. 92, 482 (1953). - KARPLUS, KLEIN and SCHWINGER: Phys. Rev. 86, 288 (1952).
R. KARPLUS and N. KROLL: Phys. Rev. 77, 536 (1950). - M. BARANGER, F. DYSON and E. SALPETER: Phys. Rev. 88, 680 (1952). - BERSOHN, WENESER and KROLL: Phys. Rev. 91, 1257 (1953).
S. TRIEBWASSER, E. DAYHOFF and W. LAMB: Phys. Rev. 89, 98 (1953).
R. NOVICE, E. LIPWORTH and P. YERGIN: Phys. Rev. 100, 1153 (1955).
See ref. [16), Chap. 4.
Classically speaking, s and k precess rapidly about the direction of M. In turn, M precesses about the direction of f, but much more slowly, and only the components of s and k parallel to M are important.
S. ToLANSxl: Fine Structure In Line Spectra. London: Methuen and Co. 1935.
G. BREIT: Phys. Rev. 35, 1447 (1930).
In fact, the anomalous magnetic moment of the electron was first inferred from a discrepancy between (22.14) and experiment. G. BREIT: Phys. Rev. 72, 984 (1947).
R. KARPLUS and A. KLEIN: Phys. Rev. 85, 972 (1952). — N. M. KROLL and F. POLL0cK: Phys. Rev. 86, 876 (1952).
G. BREIT and R. MEYEROTT: Phys. Rev. 72, 1023 (1947).
R. ARNOWITT: Phys. Rev. 92, 1002 (1953). — W. NEWCOMB and E. SALPETER: Phys. Rev. 97, 1146 (1955).
A. PRODELL and P. KuscH: Phys. Rev. 88, 184 (1952) and 100, 1183 (1955). — J. WITKE and R. DICKE: Phys. Rev. 96, 530 (1954).
S. KOENIG, A. PRODELL and P. KuscH: Phys. Rev. 88, 191 (1952). — R. BERINGER and M. HEALD: Phys. Rev. 95, 1474 (1954).
The internal structure of the proton also contributes (unknown) corrections to the fine structure separation energy of the same absolute order of magnitude as to hyperfine structure. But, since the fine structure itself is very much larger than hyperfine structure, these corrections have a negligible effect on (21.6), but an appreciable one on (22.20). On the other hand, the purely experimental errors are larger in the experiments leading to (21.6) than in those leading to (22.20).
A. BOHR: Phys. Rev. 73, 1109 (1948). — F. E. Low: Phys. Rev. 77, 361 (1950). — F. Low and E. SALPETER: Phys. Rev. 83, 478 (1951).
C. GREIFINGER: Ph. D. Thesis, Cornell 1954.
For a more detailed account and a bibliography see a review article by S. DEBENEDETTI and H. C. CORBEN, Ann. Rev. Nuc. Sci. 4, 191 (1954). Cf. also L. SIMONS in Vol. XXXIV of this Encyclopedia.
A. ORE and J. POWELL: Phys. Rev. 75, 1696, 1963 (1953).
All terms of order as Ry were first calculated by J. PIRENNE, Arch. Sci. phys. nat. 29, 121, 207, 265 (1947); V. BERESTETSKI and L. LANDAU, J. exp. theor. Phys. USSR. 19, 673, 1130 (1949). Some errors in these papers were corrected by R. A. FERRELL, Phys. Rev. 84, 858 (1951).
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Bethe, H.A., Salpeter, E.E. (1957). The hydrogen atom without external fields. In: Quantum Mechanics of One- and Two-Electron Atoms. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-12869-5_2
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