Tight-binding-like expressions for the continuous-space electromagnetic coupling

Hamiltonian
Timothy B. Boykin

Citation: American Journal of Physics 69, 793 (2001); doi: 10.1119/1.1344169

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 Tight-binding-like expressions for the continuous-space electromagnetic
coupling Hamiltonian
Timothy B. Boykin
Department of Electrical and Computer Engineering and LICOS, The University of Alabama in Huntsville,
Huntsville, Alabama 35899
共Received 16 August 2000; accepted 10 November 2000兲
In quantum mechanics texts one sometimes encounters the unqualified 共and generally untrue兲
assertion that the solution of the Schrödinger equation for a charged particle in the presence of an
externally applied vector potential can be found from that in the absence of the vector potential
simply via multiplication with an r-dependent phase factor. The confusion caused by this assertion
is only increased when one examines the expression for the matrix elements of the Hamiltonian
including electromagnetic interactions 共via the vector potential兲 appropriate for a tight-binding
model, for this expression indeed takes a different form from that of the usual minimal coupling
Hamiltonian in continuous space. Motivated by the tight-binding 共i.e., discretized兲 result, we derive
its continuous-space analog. We show that the aforementioned perplexing assertion actually arises
from a confusion between the wavefunction and the matrix elements of the continuous-space
Hamiltonian in the position basis and discuss both the tight-binding and continuous-space
expressions. © 2001 American Association of Physics Teachers.
关DOI: 10.1119/1.1344169兴

It is sometimes 共incorrectly兲 asserted in quantum mechan-

ics texts that the solution to the Schrödinger equation for a
charged particle in the presence of the vector potential in
冋 冕
具 ␻ ;R j 兩 Ĥ 共 A兲 兩 ␻ ⬘ ;R j ⬘ 典 ⫽exp i
Q
ប
␴:R j

general may be obtained from that in the absence of the
vector potential via multiplication with an r-dependent
phase. The origin of this misunderstanding is a confusion
between the wavefunction and the matrix elements of the
Hamiltonian in the continuous basis and its resolution is the
purpose of this paper.
It is not difficult to see how such a misunderstanding
might arise, for there are perfectly correct expressions in-
volving the Hamiltonian in the presence of a vector potential
which, on casual inspection, can be easily misinterpreted.
Consider first the expression 共due to Feynman1兲 for the am-
plitude for a particle of charge Q to go from a to b along a
specified path, ␳,
␴:R j ⬘
A•dl 册
⫻具 ␻ ;R j 兩 Ĥ 0 兩 ␻ ⬘ ;R j ⬘ 典 , 共2兲
where we use a circumflex to denote operators; ␻ and ␻⬘ are
atomic-like orbitals respectively centered on atoms located at
R j and R j ⬘ ; and ␴ specifies the straight-line path R j ⬘
→R j . 2,3 The first justification of Eq. 共2兲 was based upon a
Peierls substitution and the two-center approximation 共see
Ref. 2 for a discussion of the Peierls substitution within the
context of tight-binding兲; a more detailed analysis of 共2兲,
given in Ref. 3, is far beyond the scope of this work. This
more rigorous treatment,3 by taking explicit account of the
incompleteness of the tight-binding basis,4 shows that the
straight-line path is a direct consequence of both the Hermi-
ticity of Ĥ (A) and the fact that A couples into the Hamil-

具 b 兩 a 典 A⫽s⫽exp 再 冕
iQ
ប
␳共 b 兲

␳共 a 兲
冎
A•dl 具 b 兩 a 典 A⫽0 ,
where the subscript A⫽0 (A⫽0) denotes the amplitude in
the presence 共absence兲 of the applied vector potential A.
When 共1兲 is applied to a one-dimensional tight-binding
model it is indeed true that the matrix element of the Hamil-
tonian 共between orbitals centered on sites a and b兲 in the
presence A is simply that for A⫽0 multiplied by
exp关iQ/ប兰baA(x) dx兴. Feynman of course recognizes that in
this one-dimensional model there can be no ambiguity of
path and his result is therefore rigorously correct.
More pertinently, observe that a similar expression results
for three-dimensional tight-binding models, even though
such a result would seem to be precluded by the question of
which path ought to be taken between the sites. It can in fact
be shown that the matrix elements of the Hamiltonian in the
presence of the vector potential, Ĥ (A) , are related to those of
the bare Hamiltonian (A⫽0), Ĥ 0 , by
共1兲
tonian via the momentum operator.
Equation 共2兲 well illustrates the origin of the confusion,
for it seems, on very casual inspection, to suggest that the
solution to the Schrödinger equation for a charged particle in
the presence of the vector potential may be obtained from
that in the absence of the vector potential via multiplication
with an r-dependent phase. In reality it does nothing of the
sort, for 共2兲 makes a statement about the relationship be-
tween matrix elements of the Hamiltonian in a discretized
position basis, not solutions of the Schrödinger equation. It
does, however, suggest that an analogous expression in
continuous-space, relating the matrix elements of H 0 to those
of the Hamiltonian in the presence of vector 共A兲 and scalar
共U兲 potentials,5
1
Ĥ 共 A兲 ⫽ 关 p̂⫺QA共 r̂,t 兲兴 2 ⫹QU 共 r̂,t 兲 , 共3兲
2m
ought to exist in the continuous position ‘‘basis.’’ 共Although
our interest is in expressions involving matrix elements of
the continuous-space Hamiltonian, the motivation clearly
comes from tight-binding, so in the Appendix we discuss

793 Am. J. Phys. 69 共7兲, July 2001 http://ojps.aip.org/ajp/ © 2001 American Association of Physics Teachers 793
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 some details of a very simple tight-binding model.兲 Here we d ␳共 ␭ 兲 d f 共 ␣ 兲共 ␭ 兲
first derive an exact analog of 共2兲 for the usual 共complete-
d␭
⫽ 兺␣ e␣ d 共 ␣ 兲
d␭
, d 共 ␣ 兲 ⬟ 共 r 共 ␣ 兲 ⫺r ⬘ 共 ␣ 兲 兲 ,
basis兲 Hamiltonian 共3兲, then show how the Schrödinger
equation for Hamiltonian 共3兲 can be obtained from a Peierls- 共6兲
like substitution. where e␣ are the Cartesian unit vectors and we denote com-
To develop an exact analog of 共2兲 we note that the basis ponents with superscripts; we leave the f ( ␣ ) unspecified in
states employed there are localized on specific atomic sites: the development below since our derivation must hold for
since 共3兲 applies in continuous space, this suggests we em- any path. 共Note, however, that the special case of a straight
ploy the 兵兩r典其-representation. Because this ‘‘basis’’ is con- line corresponds to f ( ␣ ) ⫽ f , ␣ ⫽x,y,z, and that in this in-
tinuous, orthogonality relations will involve the Dirac delta stance the parameter ␭ becomes superfluous, as it can with-
function instead of the Kroenecker delta, so that our analog out loss of generality be dropped in preference to f.兲 To
of 共2兲 must hold in the sense of a generalized function, de- express the line integral of 共4兲 along the 共general兲 path we
fined by its action on a test function. Keeping 共1兲 and 共2兲 in employ the average of the Taylor expansions of A( ␳) taken
mind, it is not difficult to deduce the analog. Intuitively we about the two endpoints:
expect, and will demonstrate below, that the relation
A 共 ␣ 兲 „␳共 ␭ 兲 …

具 r兩 Ĥ 共 A兲 兩 r⬘ 典 ⫽exp i 冋 冕 Q
ប
r

r⬘
册
A共 s,t 兲 •ds 具 r兩 Ĥ 0 兩 r⬘ 典 共4兲
⫽
1
2 再
关 A 共 ␣ 兲 共 r⬘ 兲 ⫹A 共 ␣ 兲 共 r兲兴 ⫹ 兺␤ d 共 ␤ 兲
holds in the 兵兩r典其-representation. Because the basis is con-
tinuous and the representation of Ĥ 0 therein involves only
repeated 共not mixed兲 second-partial derivatives, the line in-
⫻ 冋冋 冏 ⳵A共␣兲
⳵␳ 共 ␤ 兲 r⬘
f 共 ␤ 兲共 ␭ 兲 ⫺ 冋 冏
⳵A共␣兲 共␤兲
⳵␳ 共 ␤ 兲 r
g 共␭兲 册
tegral in 共4兲 can be taken along any path.6
To establish 共4兲, we begin by expressing a general path
between points r and r⬘ in parametrized form as:
⫹
1
2! 兺
␤,␥
d 共 ␤ 兲d 共 ␥ 兲 冋冋 ⳵ 2A共␣兲
⳵␳ 共 ␤ 兲 ⳵␳ 共 ␥ 兲
冏 r⬘
f 共 ␤ 兲共 ␭ 兲 f 共 ␥ 兲共 ␭ 兲

␳共 ␭ 兲 ⫽ 兺␣ e␣ 关 r ⬘ 共 ␣ 兲 ⫹ f 共 ␣ 兲 共 ␭ 兲共 r 共 ␣ 兲 ⫺r ⬘ 共 ␣ 兲 兲兴 ,
⫹ 冋 ⳵ A 2 共␣兲

⳵␳ 共 ␤ 兲 ⳵␳ 共 ␥ 兲 r
冏
g 共 ␤ 兲 共 ␭ 兲 g 共 ␥ 兲 共 ␭ 兲 ⫹¯ , 册 冎 共7兲

共5兲 where g ( ␣ ) (␭)⬟1⫺ f ( ␣ ) (␭). Using 共7兲, we therefore find for

共␣兲 共␣兲
␭:0→1, f 共 0 兲 ⫽0, f 共 1 兲 ⫽1, ␣ 苸 兵 x,y,z 其 , the line integral in 共4兲

S共 r⬘ ,r,t 兲 ⬟ 冕 0
1
A„␳共 ␭ 兲 …
d␳
d␭
d␭⫽
1
2 再兺 ␣
d 共 ␣ 兲 关 A 共 ␣ 兲 共 r⬘ 兲 ⫹A 共 ␣ 兲 共 r兲兴 ⫹ 兺冋冋 冏 冉 冕
␣,␤
d 共 ␣ 兲d 共 ␤ 兲
⳵A共␣兲
⳵␳ 共 ␤ 兲 r⬘ 0
1
f 共 ␤ 兲共 ␭ 兲
d f 共␣兲
d␭
d␭ 冊
⫺ 冋 冏 冉冕
⳵A共␣兲
⳵␳ 共 ␤ 兲 r
1

0
g 共 ␤ 兲共 ␭ 兲
d f 共␣兲
d␭
d␭ 冊册 兺 ⫹
1
冋冋
2! ␣ , ␤ , ␥
d 共 ␣ 兲d 共 ␤ 兲d 共 ␥ 兲
⳵ 2A共␣兲
⳵␳ 共 ␤ 兲 ⳵␳ 共 ␥ 兲
冏 r⬘

⫻ 冉冕 0
1
f 共 ␤ 兲共 ␭ 兲 f 共 ␥ 兲共 ␭ 兲
df
d␭
共␣兲
d␭ ⫹
⳵ A
冊 冋 冏 冉冕
⳵␳ 共 ␤ 兲 ⳵␳ 共 ␥ 兲
2 共␣兲

r
1

0
g 共 ␤ 兲共 ␭ 兲 g 共 ␥ 兲共 ␭ 兲
df
d␭
共␣兲
d␭ 冊册 冎 ⫹¯ ,

共8兲

where in 共8兲 we suppress the time dependence of the com-

ponents of A to simplify the notation.7
Now in the 兵兩r典其-representation the matrix elements of the
冕 ⫺⬁
⫹⬁
␦ 共 n 兲 共 ␨ 兲 F 共 ␨ 兲 d ␨ ⫽ 共 ⫺1 兲 n F 共 n 兲 共 0 兲 , n⫽0,1,2,... .

bare Hamiltonian involve the Dirac delta function and its 共10兲
second derivative, so that 共4兲 must hold in the sense of a
For 共4兲 to hold we must show that
generalized function. Specifically, these matrix elements are

具 r兩 Ĥ 0 兩 r⬘ 典 ⫽⫺
ប2 共2兲 共x兲
关 ␦ 共 d 兲␦共 d共y兲兲␦共 d共z兲兲
具 r兩 Ĥ 共 A兲 兩 ␺ 共 t 兲 典 ⫽ 冕具 r兩 Ĥ 共 A兲 兩 r⬘ 典具 r⬘ 兩 ␺ 共 t 兲 典 d 3 r ⬘

冕
2m
⫹ ␦ 共 d 共 x 兲 兲 ␦ 共 2 兲共 d 共 y 兲 兲 ␦ 共 d 共 z 兲 兲 ⫽ exp关 iQS共 r⬘ ,r,t 兲 /ប 兴

⫹ ␦ 共 d 共 x 兲 兲 ␦ 共 d 共 y 兲 兲 ␦ 共 2 兲共 d 共 z 兲 兲 ] ⫻具 r兩 Ĥ 0 兩 r⬘ 典 ␺ 共 r⬘ ,t 兲 d 3 r ⬘ , 共11兲
共x兲 共y兲 共z兲
⫹QU 共 r⬘ ,t 兲 ␦ 共 d 兲␦共 d 兲␦共 d 兲, 共9兲
where the left-hand side is nothing more than Ĥ (A) ␺ (r,t);
where ␦ (2) is defined by the general relation8 Ĥ 0 ⫽Ĥ (A⫽0) ; and Ĥ (A) is given in 共3兲. To evaluate the right-

794 Am. J. Phys., Vol. 69, No. 7, July 2001 Timothy B. Boykin 794
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 hand side of 共11兲, observe that S(r,r,t)⫽0 since 关d ( ␣ ) 兩 r⬘ ⫽r tives of the Dirac delta function 共but no mixed-partials兲 the
⫽0. Also, from the ␦ (2) (d (x) ) term of 共9兲 note that line integral in 共4兲 and 共5兲 is indeed independent of path. The
path independence in the continuous basis is intuitively sat-
⫺
ប2
2m
冕␦ 共2兲
共 d共x兲兲␦共 d共y兲兲␦共 d共z兲兲
isfying as well, for the effect of the ␦ (2) and ␦ functions is to
set the length of the path of integration to zero after taking
derivatives.
⫻exp关 iQS共 r⬘ ,r,t 兲 /ប 兴 ␺ 共 r⬘ ,t 兲 d 3 r ⬘ The continuous-space analog of 共2兲, Eq. 共4兲, is also helpful

⫽⫺
ប2
2m
⫺
Q ⳵S
ប ⳵ r ⬘共 x 兲 冋冉冋 冏 冊 r⬘ ⫽r
2
␺ 共 r,t 兲
for showing how the Schrödinger equation for Hamiltonian
共3兲 can be seen to arise from a Peierls-like substitution in the
appropriate limit. Define two paths

⫹i
2Q ⳵ S
冋 冏
ប ⳵ r ⬘共 x 兲 r⬘ ⫽r
⳵ ␺ 共 r,t 兲
⳵r共x兲
⫹i
Q ⳵ 2S
ប ⳵ r ⬘共 x 兲2冋 冏 ␺ 共 r,t 兲
r⬘ ⫽r
␲ 共 ␣ 兲 共 ␭ 兲 ⫽r 共0␣ 兲 ⫹b 共 ␣ 兲 共 ␭ 兲共 r 共 ␣ 兲 ⫺r 共0␣ 兲 兲 ;
␭:0→1; b 共 ␣ 兲 共 0 兲 ⫽0; b 共 ␣ 兲 共 1 兲 ⫽1,
共16兲

⫹
⳵ 2 ␺ 共 r,t 兲
⳵ r 共 x 兲2
. 册 共12兲 ␬ 共 ␣ 兲 共 ␭ 兲 ⫽r 共0␣ 兲 ⫹c 共 ␣ 兲 共 ␭ 兲共 r ⬘ 共 ␣ 兲 ⫺r 共0␣ 兲 兲 ;
␭:0→1; c 共 ␣ 兲 共 0 兲 ⫽0; c 共 ␣ 兲 共 1 兲 ⫽1,
共17兲
It is therefore apparent that only the single and double sums
where r0 is an arbitrary point and ␣ 苸 兵 x,y,z 其 . Furthermore,
of 共8兲 can contribute to 共12兲 due to the presence of at least
define line integrals along these paths
one factor 关 d ( ␣ ) 兴 r⬘ ⫽r⫽0; no mixed ( ␣ ⫽ ␤ ) terms will sur-
vive for the same reason;9 the double sum in 共8兲 need be
fully evaluated only for the second partial of S in 共12兲; and S␲ 共 r0 ,r,t 兲 ⬟ 冕 0
1
A„␲共 ␭ 兲 …•
d ␲共 ␭ 兲
d␭
d␭,
only the ␣ ⫽x term of the single sum in 共8兲 survives. Taking
共18兲
these observations together, we find
S␬ 共 r0 ,r⬘ ,t 兲 ⬟ 冕 1
A„␬共 ␭ 兲 …•
d ␬共 ␭ 兲

冋 冏
d␭
⳵S 0 d␭
共x兲
⫽⫺A 共 r,t 兲
⳵ r ⬘共 x 兲 r⬘ ⫽r
in a manner analogous to 共8兲. Using these paths, we evaluate
the matrix element of the bare Hamiltonian under a Peierls-
and 共13兲 like transformation:

冋 ⳵ 2S
⳵ r ⬘共 x 兲2
冏 r⬘ ⫽r
⫽⫺
⳵ A 共 x 兲 共 r,t 兲
⳵r共x兲
,
具 r兩 exp关 iQS␲ 共 r0 1̂,r̂,t 兲 /ប 兴 Ĥ 0
⫻exp关 ⫺iQS␬ 共 r0 1̂,r̂,t 兲 /ប 兴 兩 r⬘ 典
so that we have for 共12兲 ⫽exp关 iQS共 r0 ,r,t 兲 /ប 兴 exp关 ⫺iQS␬ 共 r0 ,r⬘ ,t 兲 /ប 兴

⫺
ប2
2m
冕␦ 共2兲
共 d共x兲兲␦共 d共y兲兲␦共 d共z兲兲 ⫻ 具 r兩 Ĥ 0 兩 r⬘ 典 , 共19兲
where 1̂ denotes the identity operator, r̂ the position operator,
⫻exp关 iQS共 r⬘ ,r,t 兲 /ប 兴 ␺ 共 r⬘ ,t 兲 d 3 r ⬘ and we used the eigenvalue relations for the position opera-
ប 2 ⳵ 2 ␺ 共 r,t 兲 Q 2 共 x 兲 Q tor to obtain
⫽⫺ ⫹ 关 A 共 r,t 兲兴 2 ␺ 共 r,t 兲 ⫺
2m ⳵ r 共 x 兲 2 2m 2m 具 r兩 exp关 iQS␲ 共 r0 1̂,r̂,t 兲 /ប 兴 ⫽exp关 iQS␲ 共 r0 ,r,t 兲兲 /ប 兴 具 r兩 共20兲
Q 共x兲 共x兲 exp关 ⫺iQS␬ 共 r0 1̂,r̂,t 兲 /ប 兴 兩 r⬘ 典
⫻A 共 x 兲 共 r,t 兲 p̂ 共 x 兲 ␺ 共 r,t 兲 ⫺ p̂ 关 A 共 r,t 兲 ␺ 共 r,t 兲兴 ,
2m
⫽ 兩 r⬘ 典 exp关 ⫺iQS␬ 共 r0 ,r⬘ ,t 兲 /ប 兴 . 共21兲
共14兲
Next, we examine 共19兲 in the limit r0 →r:
where we have used p̂ (x) →(ប/i) ⳵ / ⳵ r (x) . Analogous terms of
course result for y and z and the U(r,t) term is trivially lim 兵 具 r兩 exp关 iQS共 r0 1̂,r̂,t 兲 /ប 兴 Ĥ 0
r0 →r
handled. Using 共14兲 and its y and z analogs, we find for 共11兲

具 r兩 Ĥ 共 A兲 兩 ␺ 共 t 兲 典 ⫽ 冕 exp关 iQS共 r⬘ ,r,t 兲 /ប 兴

⫻exp 关 ⫺iQS␬ 共 r0 1̂,r̂,t 兲 /ប 兴 兩 r⬘ 典 其
⫽exp 关 ⫺iQS␬ 共 r,r⬘ ,t 兲 /ប 兴 具 r兩 H 0 兩 r⬘ 典 , 共22兲
⫻具 r兩 Ĥ 0 兩 r⬘ 典 ␺ 共 r⬘ ,t 兲 d 3 r⬘ where the integral along the path ␲ vanishes since in the

冋 冋 册 册
limit its length is zero. Note that Eq. 共22兲 is really nothing
1 ប 2
more than the right-hand side of 共4兲 since the negative of the
⫽ ⵜ⫺QA共 r,t 兲 ⫹QU 共 r,t 兲 ␺ 共 r,t 兲 ,
2m i path integral from r to r⬘ 关as in 共22兲兴 is simply the positive
共15兲 integral along the same path going in the opposite direction,
i.e., from r⬘ to r 关as in 共4兲兴. Since we have already shown
which is nothing more than the coordinate-space Schrödinger that, regardless of path, 共4兲 gives the same Schrödinger equa-
equation for Hamiltonian 共3兲. Equation 共15兲 therefore estab- tion as does the usual minimal-coupling Hamiltonian 共3兲, this
lishes the link between the continuous and tight-binding 共i.e., derivation establishes that the minimal-coupling Hamiltonian
discretized兲 bases. Since in the continuous basis the matrix 共3兲 is indeed obtainable via a Peierls-like substitution in the
elements 具 r兩 Ĥ 0 兩 r⬘ 典 and 具 r兩 Ĥ (A) 兩 r⬘ 典 involve second deriva- appropriate limit.

795 Am. J. Phys., Vol. 69, No. 7, July 2001 Timothy B. Boykin 795
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 Finally, we briefly discuss some of the physics responsible
for the straight-line path required in the tight-binding expres-
sion 共2兲 from the perspective of our continuous-space ana-
logs developed here; the interested reader is referred else-
where for a detailed derivation.3 In the calculations above,
we noted that for both the continuous-space analog of 共2兲
and the Peierls-like substitution 共22兲 the paths are arbitrary.
This is sensible as the vector potential couples into the
Hamiltonian via the momentum operator which, in continu-
ous space, corresponds to differentiation. Now consider a
tight-binding model; once again we should find that the vec-
tor potential couples into the Hamiltonian via the momentum
operator.10 In tight-binding, however, the momentum matrix
elements take the form4,11
im 共 ␣ 兲
共␣兲
具 ␻ ;R j 兩 p̂ 共 ␣ 兲 兩 ␻ ⬘ ;R j ⬘ 典 ⫽⫺ 共 R j ⫺R j ⬘ 兲
ប p y ,p z ,etc. 其 , but the derivations require considerable ma-
⫻具 ␻ ;R j 兩 Ĥ 0 兩 ␻ ⬘ ;R j ⬘ 典 .
In 共23兲 there appears the finite difference between the
␣-components of the atomic sites. Observe that it is this dif-
ference which appears in the line integral 共8兲 共under r→R j
and r⬘ →R j ⬘ 兲, with equal weights on corresponding coeffi-
cients evaluated at the two sites for a straight line, so that the
vector potential couples to the momentum uniformly 共see
Ref. 7 as well兲. Thus the path independence in continuous-
space and straight line required in tight-binding can be
viewed as manifestations of the representation of the mo-
mentum operator in the two bases.
In conclusion, we have shown how to obtain an exact
analog of the tight-binding expression for Hamiltonian ma-
trix elements in the presence of the vector potential using the
兵 兩 r典 其 -representation. We have seen as well that in the appro-
priate limit the usual minimal-coupling Hamiltonian in con-
tinuous space can be derived as a limit of a Peierls-like sub-
stitution. We have therefore established a link between tight-
binding and continuous-space representations.
ACKNOWLEDGMENTS
I gratefully acknowledge NASA-JPL for supporting this
work and thank Chris Bowen and Gerhard Klimeck for in-
teresting discussions.
APPENDIX: TIGHT-BINDING MODELS
Although explaining the intricacies of tight-binding mod-
els in general, and the derivation of 共2兲 in particular, is far
beyond the scope of this paper, we can nevertheless see why
some of the results from tight-binding presented in the main
text ought to hold by examining the relationship between a
very simple, single-band, tight-binding model and the dis-
cretized effective-mass Schrödinger equation. Because the
underlying crystal for the tight-binding model is a simple
cubic lattice with one atom per unit cell and the basis con-
sists of a single s-like orbital centered on each site, these two
models have identical equations of motion in the absence of
a magnetic field.
Before proceeding further, we remark that while a multi-
band tight-binding model such as one uses for realistic band-
structure calculations is also discretized, in the sense that
matrix elements of observables are projected onto basis
states centered on atomic sites, it is not possible to relate the
equations of motion to a single, discretized differential equa-
796 Am. J. Phys., Vol. 69, No. 7, July 2001
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tion for two reasons: First, the crystal employed 共which plays
the role of a discretization mesh兲 depends upon the material
being modeled. Second, the basis consists of several differ-
ent atomic-like orbitals per site, so that for a perfect bulk
crystal 共one in which translational symmetry exists in all
three dimensions and over which cyclic boundary conditions
are imposed兲 the expectation value of the Hamiltonian
共which mixes basis states兲 is no longer a scalar, but is instead
a matrix. Thus the wavefunction is now a superposition of
different atomic-like orbitals. For example, the simplest
multi-band model for silicon 共two atoms per unit cell兲 has
one s- and three p-like orbitals per site if the spin-orbit in-
teraction is neglected, and double these numbers if it is in-
cluded, respectively yielding 8⫻8 or 16⫻16 matrices. Re-
sults such as 共2兲 and 共23兲 above can be shown to hold
rigorously in multi-band models where ␻,␻ ⬘ 苸 兵 s,p x ,
共23兲 chinery far beyond the scope of this paper. It is for this
reason that we treat the simple single-band model below.
In the single-band tight-binding model the atomic posi-
tions are indicated by the direct lattice vectors:
Rl,m,n ⬟a 共 lex ⫹mey ⫹nez 兲 , l,m,n integers, 共A1兲
where a is the unit cell cube edge. There is a single s-like
orbital centered on each site; those on different sites are or-
thogonal:
具 s;Rl,m,n 兩 s;Rl ⬘ ,m ⬘ ,n ⬘ 典 ⫽ ␦ l,l ⬘ ␦ m,m ⬘ ␦ n,n ⬘ . 共A2兲
The matrix elements of the Hamiltonian,
p̂2
Ĥ 0 ⫽ ⫹V 共 r̂兲 ⫹U 共 r̂兲 , 共A3兲
2m
which includes crystal 关 V(r⫹Rl,m,n )⫽V(r) 兴 and external
共U兲 potentials, in this basis are
具 s;Rl,m,n 兩 Ĥ 0 兩 s;Rl ⬘ ,m ⬘ ,n ⬘ 典
⫽ ␦ l,l ⬘ ␦ m,m ⬘ ␦ n,n ⬘ 共 E l,m,m ⫹U l,m,n 兲
⫺V l ⬘ ,m ⬘ ,n ⬘ 共 ␦ l ⬘ l⫾l ␦ m ⬘ ,m ␦ n ⬘ ,n ⫹ ␦ l,l ⬘ ␦ m ⬘ ,m⫾1 ␦ n ⬘ ,n
⫹ ␦ l,l ⬘ ␦ m ⬘ ,m ␦ n ⬘ ,n⫾1 兲 , 共A4兲
and we write the wavefunction as:
兩␺典⫽ 兺
l ⬘ ,m ⬘ ,n ⬘
C l ⬘ ,m ⬘ ,n ⬘ 兩 s;Rl ⬘ ,m ⬘ ,n ⬘ 典 , 共A5兲
where the C are expansion coefficients and the summation is
over all sites in the crystal. In 共A4兲 note that the V l ⬘ ,m ⬘ ,n ⬘ and
E l,m,n are the matrix elements of 关 p̂2 /2m⫹V(r̂) 兴 .
In order to compare tight-binding and effective-mass mod-
els, we choose tight-binding parameters appropriate for bulk
共uniform material throughout兲 and describe a conduction
band 共upward curvature兲 of effective mass m * , by setting
ប2
V l,m,n ⫽V s ⫽ , E l,m,n ⫽E s ⫽6V s , ᭙l,m,n.
2m * a 2
共A6兲
Using 共A2兲, 共A4兲, and 共A5兲, we find the projection of the
Schrödinger equation onto the orbital 兩 s;Rl,m,n 典 :
Timothy B. Boykin 796
 具 s;Rl,m,n 兩 关 Ĥ 0 ⫺1̂E 兴 兩 ␺ 典 Similarly, Taylor’s theorem for the effective-mass wavefunc-
tion gives

冋 冏
ប2
⫽C l,m,n 共 U l,m,n ⫺E 兲 ⫺ 兵 关 C l⫹1,m,n ⫺2C l,m,n ⳵␺ 1
2m * a 2 ⬇ 关␺ ⫺ ␺ l⫺1,m,n 兴 , 共A14兲
⳵x l,m,n
2a l⫹1,m,n
⫹C l⫺1,m,n 兴 ⫹ 关 C l,m⫹1,n ⫺2C l,m,n ⫹C l,m⫺1,n 兴
so that the velocity of the effective-mass wavefunction at
⫹ 关 C l,m,n⫹1 ⫺2C l,m,n ⫹C l,m,n⫺1 兴 其 . 共A7兲 共al,am,an兲 is given by

冋 冏
Boundary conditions appropriate to the problem of interest
are imposed on 共A7兲 by placing requirements on certain of ប ⳵␺ x兲
ប
⫽ ␯ 共l,m,n ⫽ 关␺ ⫺ ␺ l⫺1,m,n 兴 ,
the C l,m,n . For example, hard-wall conditions involve setting im * ⳵ x l,m,n
i2m * a l⫹1,m,n
the C l,m,n at the boundaries to zero; for bulk periodic condi- 共A15兲
tions may be enforced.
Equation 共A7兲 is in the form of a finite-difference equation where we drop the approximate equality as in 共A11兲. Thus
for the single-band, effective-mass Hamiltonian. To see this, we see that there is a close relationship between this simplest
we discretize the single-band, effective-mass Schrödinger of tight-binding models and the familiar, discretized
equation, effective-mass Schrödinger equation.
It is also interesting to see how a uniform magnetic 共B
ប2 2 ⫽B 0 ey , A⫽B 0 zex 兲 field enters the simple tight-binding
⫺ ⵜ ␺ 共 x,y,z 兲 ⫹U 共 x,y,z 兲 ⫽E ␺ 共 x,y,z 兲 , 共A8兲
2m * model. Here, we consider a crystal which is bulk-like in the
on a uniform cubic mesh of spacing a by using Taylor’s x-y plane, over which we apply Born–von Kàrman 共peri-
theorem to approximate for x 共with analogous expressions odic兲 boundary conditions 共A is a function of z only and
for y and z兲: hence does not disrupt the planar symmetry兲. Let N 储 denote

冋 冏
the number of cells in the plane; from Bloch’s theorem we
⳵ 2␺ 1 know that the eigenstates of the Hamiltonian will be simul-
⬇ 关␺ ⫺2 ␺ l,m,n ⫹ ␺ l⫺1,m,n 兴 , 共A9兲
⳵x2 l,m,n
a 2 l⫹1,m,n taneous eigenstates of the direct-lattice planar translation op-
erators so that the appropriate basis is
where we introduce the shorthand notation
Ns
1
f l,m,n ⬟ f 共 al,am,an 兲 共A10兲 兩 s;L;k储 典 ⫽
冑N 储
兺
j⫽1
exp 关 ik储 •R j, 储 兴 兩 s;L;R j, 储 典 , 共A16兲
for any function f (x,y,z). The result is
ប2 where once again the subscript 储 denotes a vector lying in the
共 U l,m,n ⫺E 兲 ␺ l,m,n ⫺ 兵 关 ␺ l⫹1,m,n ⫺2 ␺ l,m,n ⫹ ␺ l⫺1,m,n 兴 plane; R j, 储 is the projection of 共A1兲 onto the plane; k储 is the
2m * a 2 wavevector 共i.e., planar translation eigenvalue兲; and L is the
⫹ 关 ␺ l,m⫹1,n ⫺2 ␺ l,m,n ⫹ ␺ l,m⫺1,n 兴 layer index 共i.e., the z-coordinate of an atom in layer L is
La兲. The wavefunction is now written as just a sum over
⫹ 关 ␺ l,m,n⫹1 ⫺2 ␺ l,m,n ⫹ ␺ l,m,n⫺1 兴 其 ⫽0 共A11兲 layers
which is simply 共A7兲 under the replacement C l ⬘ ,m ⬘ ,n ⬘
→ ␺ l ⬘ ,m ⬘ ,n ⬘ . This is naturally anticipated, as 共A9兲 together 兩 ␺ k储典 ⫽ 兺 C L ⬘ 兩 s;L ⬘ ;k 典 . 储 共A17兲
with its y- and z-analogs is 共up to constants兲 nothing more L ⬘
than the projection of the envelope-function kinetic energy Using 共2兲, the Schrödinger equation in the planar-orbital ba-
operator onto the ‘‘basis function’’ 兩al,am,an典 in the position sis 共for an otherwise bulk-like crystal兲 reads

冋
representation. This development also demonstrates the in-
completeness of this tight-binding basis:4 it is clearly a dis-
cretized form of the 共continuous兲 position ‘‘basis’’ 兵 兩 r典 其 . ⫺V s C L⫺1 ⫹ E s ⫺2V s cos 共 k y a 兲

冋冉 冊册 册
A similar analogy obtains for the velocity operators; we
compare them instead of the momentum operators since the eB 0 La
envelope-function cannot describe the full momentum as ⫺2V s cos k x⫹ a ⫺E C L ⫺V s C L⫹1 ⫽0,
ប
does the true wavefunction, 共A5兲. Using 共23兲 we find for the
velocity matrix elements in the single-s-like orbital tight- 共A18兲
binding model,
where we take the external scalar potential U⫽0 and the
p̂ 共 x 兲 charge of the electron is ⫺e; as with 共A7兲 boundary condi-
具 s;Rl,m,n 兩 兩 s;Rl ⬘ ,m ⬘ ,n ⬘ 典 tions are expressed in terms of the C L . Equation 共A18兲
m
shows that the effect of a uniform field is just a layer-
ប dependent shift of the x-component of the wavevector.
⫽ 共 l ⬘ ⫺l 兲共 ␦ l ⬘ ,l⫹1 ⫹ ␦ l ⬘ ,l⫺1 兲 ␦ m ⬘ ,m ␦ n ⬘ ,n , 共A12兲 Peierls’ original conjecture was in fact that in a magnetic
i2m * a
field the energy of an electron in a band of dispersion E n (k)
so that the projection of 共A5兲 onto the orbital 兩 s;R l,m,n 典 is is given by the solution of the equation
simply
E n 关共 p̂⫹eA兲 /ប 兴 ␺ ⫽E ␺ , 共A19兲
p̂ 共 x 兲 ប
具 s;Rl,m,n 兩 兩␺典⫽ 共C ⫺C l⫺1,m,n 兲 .
where the operator on the left-hand side of 共A19兲 is formed
m i2m * a l⫹1,m,n
共A13兲 by replacing k→(p̂⫹eA)/ប in E n (k). 12

797 Am. J. Phys., Vol. 69, No. 7, July 2001 Timothy B. Boykin 797
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 1
Richard P. Feynman, Robert B. Leighton, and Matthew Sands, The Feyn- r ⬘ ( ␣ ) ⫽r ( ␣ ) so that the coordinates r⬘ are therefore general.
man Lectures in Physics, Vol. III 共Addison-Wesley, Reading, MA, 1965兲, 7
Note that in general only the straight-line path guarantees equal magnitude
pp. 21-1–21-3.
2 coefficients for the components of A evaluated at r and r⬘ ; in the discrete
M. Graf and P. Vogl, ‘‘Electromagnetic fields and dielectric response in
empirical tight-binding theory,’’ Phys. Rev. B 51, 4940–4949 共1995兲. tight-binding basis this is necessary if Ĥ (A) is to be an Hermitian operator.
3
Timothy B. Boykin, R. Chris Bowen, and Gerhard Klimeck, ‘‘Electromag- For example, if f (x) (␭)⫽ f (y) (␭)⫽␭, f (z) (␭)⫽␭ 2 we find for the term of
2 1
the double sum in 共8兲 3 关 ⳵ A / ⳵␳ 兩 r⬘ ⫺ 3 关 ⳵ A / ⳵␳ 兩 r whereas the
netic coupling and gauge invariance in the empirical tight-binding (z) (x) (z) (x)

method,’’ Phys. Rev. B 共in press兲. straight-line path gives

1
for this term 2 关关 ⳵ A / ⳵␳ 兩 r⬘ ⫺ 关 ⳵ A (z) / ⳵␳ (x) 兩 r兴 .
(z) (x)
4
Timothy B. Boykin, ‘‘Incorporation of incompleteness in the kp perturba- 8
M. J. Lighthill, An Introduction to Fourier Analysis and Generalised
tion theory,’’ Phys. Rev. B 52, 16317–16320 共1995兲.
5 Functions 共Cambridge U.P., New York, 1958兲, p. 19.
Claude Cohen-Tannoudji, Bernard Diu, and Franck Lalöe, Quantum Me-
chanics, translated by Susan Reid Hemley, Nicole Ostrowsky, and Dan
9
Specifically, observe that 兰 ␦ (2) (r (x) ⫺r ⬘ (x) ) ␦ (r (y) ⫺r ⬘ (y) ) ␦ (r (z) ⫺r ⬘ (z) )
Ostrowsky 共Wiley, New York, 1977兲, pp. 315–328. ⫻(r (y) ⫺r ⬘ (y) )F(r⬘ )d 3 r ⬘ ⫽0 due to the factor (r (y) ⫺r ⬘ (y) ) ␦ (r (y) ⫺r ⬘ (y) ).
10
6
By path we mean a simple curve, one which does not intersect itself, and Recall that in the Hamiltonian formulation of classical mechanics as well
we also exclude paths which become closed curves as r⬘ →r: Observe that the vector potential enters the equations of motion with the momentum.
the parametrized path 共5兲 explicitly precludes even simple closed curves.
11
Equation 共23兲 holds so long as the spin-orbit Hamiltonian is assumed to
While it is true that the path 共5兲 reduces to a straight line when, for have only same-site matrix elements; see Refs. 2 and 3 and references
example, r ⬘ (x) ⫽r (x) and r ⬘ (y) ⫽r (y) , it must be recognized that r⬘ cannot therein for details.
be so fixed with respect to r since we must integrate out the coordinates 12
Joseph Callaway, Quantum Theory of the Solid State, student ed. 共Aca-
r⬘ . Indeed the functions ␦ (2) (r ( ␣ ) ⫺r ⬘ ( ␣ ) ) take derivatives prior to setting demic, San Diego, 1974兲, sec. 6.2.3.

WATTS, AMPERES, AND ERGS

Education ran riot at Chicago, at least for retarded minds which had never faced in concrete
form so many matters of which they were ignorant. Men who knew nothing whatever—who had
never run a steam-engine, the simplest of forces—who had never put their hands on a lever—had
never touched an electric battery—never talked through a telephone, and had not the shadow of a
notion what amount of force was meant by a watt or an ampère or an erg, or any other term of
measurement introduced within a hundred years—had no choice but to sit down on the steps and
brood as they had never brooded on the benches of Harvard College, either as student or professor,
aghast at what they had said and done in all these years, and still more ashamed of the childlike
ignorance and babbling futility of the society that let them say and do it.

Henry Adams, The Education of Henry Adams 共The Modern Library, New York, 1931—Originally published by the
Massachusetts Historical Society, 1918兲, p. 342.

798 Am. J. Phys., Vol. 69, No. 7, July 2001 Timothy B. Boykin 798
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