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JChemPhys 19 1396
JChemPhys 19 1396
PerOlov Lwdin
Citation: J. Chem. Phys. 19, 1396 (1951); doi: 10.1063/1.1748067
View online: http://dx.doi.org/10.1063/1.1748067
View Table of Contents: http://jcp.aip.org/resource/1/JCPSA6/v19/i11
Published by the American Institute of Physics.
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NOVEMBER,
1951
The solution of the quantum-mechanical eigenvalue problem is discussed for cases when a series of approximate eigenfunctions is known. If these "unperturbed" states are divided into two classes, a perturbation
formula is derived giving the influence of one class of states on the other in the final solution: The formula
contains as special cases: (i) the Schrodinger-Brillouin formula for the eigenvalue of a nondegenerate state,
(ii) a new simple formula for treating a class of degenerate states, and (iii) the splitting of the secular equation in cases where the system naturally consists of two independent parts in mutual interaction.
1. INTRODUCTION
problem
(1)
is the perturbation method due to Schrodinger. 1 In its
conventional form, the operator H has the form
H = Ho+ V, and, for the derivation of the perturbation
formulas, it is usually assumed2 that V can be expressed
as a power series in a perturbation parameter A. Another type of derivation of these formulas has been
given by Lennard-Jones3 and by Brillouin,4 who used
the secular equation and the theory of bordered determinants. Here we will show that a still simpler treatment of the perturbation theory can be given by using
the system of linear equations" corresponding to the
secular equation. Dividing the given "unperturbed"
states into two classes, we will derive a formula which
explicitly gives the influence of one class of states on
the other in the final solution of (1). As speciai cases we
will obtain the Schrodinger-Brillouin formula4 for the
eigenvalue of a nondegenerate state, a new formula for
the treatment of a class of degenerate states, and finally
a formula for the splitting of the secular equation for a
system which naturally consists of two independent
parts in mutual interaction. Even if these formulas are
here derived mainly for the application in the theory
of molecules, they may be useful in other parts of
quan tum mechanics.
(2)
For this purpose we introduce the matrix elements of
the total operator H with respect to the given set:
(3)
The coefficients Cn can now be determined by the variational principle, which says that the integral
E= !if;*Hif;dr / !if;*if;dr
(5)
n=l
1396
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PERTURBATION THEORY
3. A PERTURBATION FORMULA FOR THE MUTUAL
INFLUENCE OF TWO CLASSES OF STATES
(6)
(14)
we get then
A
(8)
Cm=
1397
afj
(9)
Ukkk_E=O.
Introducing the new notation
we get
(11)
For the two cases of m in (A) or (B), we have, therefore,
the two basic formulas
(12)
(13)
The first formula is formally identical to (5), but it is
limited only to the class (A). This gives the theorem:
Hmn= {
(17)
V mn
for
m;;en.
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1398
PER-OLOV LOWDIN
(19)
(21)
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1399
PERTURBATION THEORY
1/11(0), 1/12(0), .. '1/I6(l, and the 7r-orbital 1/17(0) of the
substituent. The matrix H has then the form:
(23)
Hll
IH17
H22
IH27
H33
IH37
H=
H66
IH67
H 73 H76
IHn
----- ----
H72
H71
(22)
Hll-E
IHl, n+!'"
HI, n+P
IH2, n+l'"
H 2, n+p
I .....
A+B
H n,
n+p
= II (Hii-E)
i
H n+!,
H n+1,
2'"
. . . . ..
H n+ p ,
H n+p ,
1
H n+ p ,
2'"
1-LL
n 1
IHT812
(E-Hrr) (E-'-H88)
+L L
n r 2 8182
HT181HTlS2112
II HT2S1HT2S2
(E-Hrlrl)(E-Hr2r2)(E-HsI81)(E-Hs282)
+ ...
11
12
0/ Determinants
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(Lon-
1400
PER-OLOV LOWDIN
(25)
\
FIG.
H rlSk
Hr281
Hr2s2
Hr2sk
Hrk81
HrkS2
Hrksk
L'lJ.
L58
Hmn= LPovamPotSjl'vam
(27)
H=atSja.
(28)
or
(26)
we get directly
Hr1S1
SjPov= fcpPo*HCP.dr
aqiJolt
aqPo2t ..
aqPok t
SjJJ1V1 SjPo1v2 .
SjiJolvk
aV1S2 .
aV1Sk
ar2JJlt
ar2JJ2t .
ar2JJkt
SjJJ2V1 Sj1'2v2 .
aV2Sk
arkl'lt
arkPo2t ..
arkPok t
SjPokV1 Sjl'kv2 .
Sjl'kVk
aVk81 aVkS2
aVk8k
aV1S1
(29)
where J.l.1 < J.l.2 < ... <J.l.k and VI < V2< .. Vk. The terms in (24) can now be factorized, and, introducing the notations
aPo1'rl .a:-'1:r2::.
l aJJk'rl
Q:lJL2"'J.l.k'=
PIP.2"
'p../t;
Tlr2"
aPok'r2
B
1II'"l"'p/c'
L:
arkiJolt
arkI'2t
arkPokt
rk
~vl.81. aV182
Q~V2"'Jlk =
IaVk81
aVk82
aVISk
I as1v1't
as1v2't
a S1vk't
aVk8k
a8kv1't
aSkv2't
aSkvk't
81 8 2"'Bk
we can write the determinant D in the left-hand side of (24) in the form
t We
note that the MO in the total system (A+B) must be chosen in such a way that they are linearly independent.
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(30)
P~RTURBATION
1401
TH~ORY
+( -l)p
p,lJ.l.2
"P.p
~PPP2
S)JJpJ'p
"1'J12"""'/
S)Jlplpl'
S)vp IJJ2'
(31)
J.l.l'P.2'oJlP'
(32)
H=
[:*
(33)
The example treated here is concerned with the oneelectron wave functions, but we wish to emphasize
that the general perturbation theory, contained in the
formulas (10), (12), and (13), even can be applied to
the molecular wave functions.
In conclusion, we wish to remark that, even if the
methods described here were partly known previously
in connection with special problems, for instance in
the radiation theory given by Gora,6 a general treatment has not yet been published. We have given not
only a simple derivation of the conventional perturbation theory, but also a new treatment of the problem
of degeneracy and of the general problem of splitting
the secular equation.
ACKNOWLEDGMENTS
The author should like to express his sincere gratitude to Professor Hertha Sponer, Department of
Physics, Duke University, for many valuable discussions and for the great hospitality he has enjoyed during
his stay in Durham, North Carolina.
APPENDIX. SYMBOLIC DERIVATION OF THE
BASIC FORMULAS
The right-hand member of (9) is simply a geometrical series
in the matrix h' belonging to the class (B), and it is therefore easy
Aa+(3b=Ea,
{ (3*a+Bb=Eb.
(34)
1
b=--R*a
E-B" ,
(35)
and
(36)
If we confine the indices of UA to the class (A), we have therefore
UAa=Ea,
1
UA=A+(3E_B(3*
(37)
(38)
UA=A+(3_1_(3*+(3_1_B,_1_(3*+""
E-Bd
E-Bd E-Bd
(39)
which is nothing but (9). Equation (37) gives then (12), and Eq.
(35) gives (13). In this way all our basic formulas are derived.
18 See, for instance, Courant-Hilbert, Methoden der Mathematischen Physik, I (Verlag. Julius Springer, Berlin, 1931), p. 16,
footnote 1.
19 Compare Gora, reference 5. For the symbolic treatment given
here, the author is indebted to a discussion with Dr. G. Goertzei,
Columbia University.
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