Mat. Res. Bull. Vol. 8, pp.

153-160,
in the United S t a t e s .

1973.

Pergamon Press,

Inc.

Printed

RESONATING V A L E N C E BONDS" A NEW KIND OF I N S U L A T O R ? *

P. W. A n d e r s o n
M u r r a y Hill, New J e r s e y 07974
and
Cavendish Laboratory, Cambridge, England

Bell L a b o r a t o r i e s ,

( R e c e i v e d D e c e m b e r 5, 1972; Invited**)

ABSTRACT
The p o s s i b i l i t y of a new kind of e l e c t r o n i c s t a t e is p o i n t e d out,
c o r r e s p o n d i n g r o u g h l y to P a u l i n g ' s idea of " r e s o n a t i n g v a l e n c e
b o n d s " in m e t a l s . As o b s e r v e d by P a u l i n g , a p u r e s t a t e of t h i s
t y p e would be i n s u l a t i n g ; it would r e p r e s e n t an a l t e r n a t i v e s t a t e
to the N6el a n t t f e r r o m a g n e t i c s t a t e for S = 1/2. An e s t i m a t e of
its e n e r g y is m a d e in one c a s e .

Many y e a r s ago P a u l i n g gave a " r e s o n a t i n g v a l e n c e bond" t h e o r y of

m e t a l s (1) w h i c h v i r t u a l l y i g n o r e d the e l e c t r o n g a s n a t u r e of the m e t a l l i c s t a t e
and i n s t e a d t r i e d to r e l a t e the b i n d i n g e n e r g i e s s e m i q u a n t i t a t i v e l y to known
v a l e n c e bond c o n c e p t s .

Only r e c e n t l y h a s t h e c o n v e n t i o n a l F e r m i g a s t h e o r y

b e g u n to a d d r e s s i t s e l f m o r e a n a l y t i c a l l y to the s a m e p r o b l e m s . But P a u l i n g ' s

a t t e m p t l e a v e s b e h i n d a v e r y i n t e r e s t i n g p r o b l e m of p r i n c i p l e :

i s a s t a t e in

w h i c h v a l e n c e bonds m o v e a r o u n d f r e e l y b e t w e e n p a i r s of a t o m s a m e t a l in
fact ? D o e s it c o n d u c t e l e c t r i c i t y in the c h a r a c t e r i s t i c

metallic way?

More

* W o r k at the C a v e n d i s h L a b o r a t o r y s u p p o r t e d in p a r t by the A i r F o r c e Office

of S c i e n t i f i c R e s e a r c h Office of A e r o s p a c e R e s e a r c h , U. S. A i r F o r c e
u n d e r g r a n t No. 1052-69.
* * T h i s p a p e r w a s o r i g i n a l l y i n t e n d e d f o r the P a u l i n g F e s t s c h r i f t ,
N u m b e r 11 ( N o v e m b e r 1972).

1.53

V o l u m e 7,

154

RESONATING V A L E N C E BONDS

Vol. 8, No. 2

f u n d a m e n t a l l y , d o e s it e x i s t ?
Pauling, of c o u r s e , gave the c o r r e c t and r a t h e r obvious a n s w e r on the
c o n d u c t i v i t y : it is not, so he s u p p l e m e n t e d his r e s o n a t i n g v a l e n c e bonds with
a f r a c t i o n of ionized s t a t e s .

The s t a t e which is d e s c r i b e d only a s a s u p e r -

position of v a l e n c e bonds cannot c o n d u c t e l e c t r i c i t y at a b s o l u t e z e r o b e c a u s e

p r e s u m a b l y t h e r e is an e n e r g y gap to any s t a t e w h i c h h a s any long r a n g e
c h a r g e f l u c t u a t i o n s , by the s t a n d a r d a r g u m e n t s which apply to the Mott i n s u l a tor.

If t h e r e w e r e zmt, it would be b e t t e r d e s c r i b e d a s a m o r e o r l e s s

strongly c o r r e l a t e d metal.
Our c o n c e r n h e r e is with the q u e s t i o n of the insulating r - v - b s t a t e
( r e s o n a t i n g - v a l e n c e - b o n d ) and with w h e t h e r o r not t h e r e c a n be a p h y s i c a l r e p r e s e n t a t i v e of t h i s s t a t e .

We m a k e the b a s i c p h y s i c a l a s s u m p t i o n of P a u l i n g ' s

e a r l y w o r k on r - v - b s t a t e s of a r o m a t i c m o l e c u l e s : that the e f f e c t of c o v a l e n t
bonding in c o n n e c t i o n with the r e p u l s i v e i n t e r a c t i o n s b e t w e e n e l e c t r o n s in the
s a m e o r b i t a l is b e s t d e s c r i b e d by what is now known a s a H e i s e n b e r g H a m i l t o n i a n and w a s t h e n c a l l e d the H e i t l e r - L o n d o n t h e o r y :
H = ~

ij JijSi "SJ"

T h i s is the s a m e a s the H a m i l t o n i a n of the spin 1/2 a n t i f e r r o m a g n e t .

(I)

We will

give a v e r y b r i e f r e p o r t h e r e of s o m e r e s u l t s on the g r o u n d s t a t e of a s y s t e m
of this kind, w h i c h s u m m a r i z e s r e s u l t s of a p a p e r now in p r e p a r a t i o n .
The g r o u n d s t a t e of m a n y m a g n e t i c m a t e r i a l s with t h r e e - d i m e n s i o n a l
l a t t i c e s and spins g r e a t e r t h a n 1/2 is known e x p e r i m e n t a l l y to be c l o s e to the
" N 6 e l " a n t i f e r r o m a g n e t i c s t a t e , in which the s p i n s a r e lined up in the a r r a n g e m e n t which c l a s s i c a l spins would a s s u m e , only d e v i a t i n g b e c a u s e of q u a n t u m
z e r o - p o i n t motion.

On the t h e o r e t i c a l side (2), the s u c c e s s of e s t i m a t e s of

e n e r g y and spin d e v i a t i o n (3), and the p h y s i c a l p l a u s i b i l i t y of the p i c t u r e of

the a n t i f e r r o m a g n e t a s a c l e a r c a s e of " b r o k e n s y m m e t r y " and of the s p i n w a v e s a s a " G o l d s t o n e m o d e " , q u e l l e d m o s t of the doubts (4) e x p r e s s e d e a r l i e r about the n a t u r e of this g r o u n d state.
The e x p e r i m e n t a l s i t u a t i o n f o r S = 1//2 is e n t i r e l y a n o t h e r m a t t e r .

Ex-

c e p t for c e r t a i n c o p p e r s a l t s and Ir c o m p l e x e s w h e r e a n i s o t r o p y is nonn e g l i g i b l e r e l a t i v e to J, t h e r e a r e n_o_oe x p e r i m e n t a l c a s e s of a n t t f e r r o m a g n e t -

Vol. 8, No. 2

ism.

RESONATING VALENCE BONDS

Characteristically,

transitions

155

l i k e VO 2 and T t 2 0 3 u n d e r g o " p a t"r"Lng "

materials

in w h i c h t h e l a t t i c e d i s t o r t s

in s u c h a w a y a s to f o r m p a i r s of d 1

tons, w h i c h a r e j o i n e d m o r e o r l e s s by a v a l e n c e bond.

But many compounds,

s u c h a s s o m e of t h e M a g n ~ l i p h a s e s and T a S 2 in t h e I T f o r m , a s w e l l a s o t h e r
l o w e r d - b a n d c o m p o u n d s ( s u c h a s VOx) s h o w e s s e n t i a l l y

mysterious

behavior.

T h e m a i n t h r u s t of o u r a r g u m e n t w i l l be to s h o w that tn at l e a s t o n e
c a s e w h e r e a N 6 e l s t a t e is l o c a l l y s t a b l e ,

the t r i a n g u l a r

layer lattice,

is a n o t h e r q u i t e d i s t i n c t g r o u n d s t a t e w h i c h is l o w e r in e n e r g y .

there

We v i s u a l i z e

t h e r e l a t i o n b e t w e e n t h e t w o a s b e i n g that of a q u a n t u m liquid vs. a q u a n t u m

solid.

The N6el s t a t e is like a s o l i d :

it h a s c o n d e n s e d into a s p i n l a t t i c e ,

w h e r e a s t h e r e a l g r o u n d s t a t e is a fluid of m o b i l e v a l e n c e b o n d s ,
spins correlated
larly,

t o g e t h e r into s i n g l e t s .

i.e.

p a i r s of

O t h e r a u t h o r s (4), M a r s h a l l p a r t i c u -

h a v e s u g g e s t e d that the g r o u n d s t a t e is d i s o r d e r e d ;

we a r e m e r e l y of_

f e t i n g new' e v i d e n c e f o r t h i s a s w e l l a s a m o r e m o d e r n point of v i e w .

The

q u e s t i o n of what is m e a n t by t w o " g r o u n d s t a t e s " f o r the s y s t e m is, I think,

p e r f e c t l y m e a n i n g f u l point"

the c l e a r e x a m p l e is e i t h e r i s o t o p e o r h e l i u m ,

w h e r e e i t h e r a s o l i d o r a liquid g r o u n d s t a t e is a v a i l a b l e ,
sity.

d e p e n d i n g on d e n -

T h e t w o s t a t e s a r e s o f a r a p a r t in p h a s e s p a c e a s to b e u n a v a i l a b l e

quantum-mechanically
dimension,

to e a c h o t h e r .

T h i s p r o b a b l y c a n n o t be the c a s e in one

s o that no r e a l l y c l e a r d i s t i n c t i o n b e t w e e n N~el s t a t e and r - v - b

liquid is l~?ssible t h e r e ; t h u s ,

in p r i n c i p l e a n i n s u l a t i n g r - v - b s t a t e d o e s e x -

ist in that c a s e .
L e t us, h o w e v e r ,

d i s c u s s the o n e - d i m e n s i o n a l

case for orientation.

The e n e r g y of a p u r e N~el s t a t e
~N~el :

(~(1)fl (2)~(3)~ (4) . . .

(2)

in t h i s c a s e is
Z S 2 = - N J ~1
U = - N J ~w h e r e a s the c o r r e c t

(3)

e n e r g y is m u c h l o w e r (5),
1
U = - N J ~- x 1. 773 : -0. 443 NJ.

A m u c h c l o s e r e s t i m a t e than eqn.
c h a i n of p a i r e d a t o m s ,

(4)

(3) can be o b t a i n e d by u s i n g an a l t e r n a t i n g

156

RESONATING VALENCE BONDS

~= (ot(1)I3 (2)-oi(2)~ (i))(34)(56)

%/~

Vol. 8, No. 2

(5)

"''

(in Hulth~n's obvious notation), which g i v e s

U -

_NJ S(S+ 1) = -0. 375 NJ.

(6)

Thus, the ground state m u s t , in s o m e s e n s e , be c l o s e r to eqn. (5) than (2).

The b e s t e s t i m a t e f r o m spin wave t h e o r y is Kubo's v a r i a t i o n a l one:
.1 396,
(Us_w)variationa 1 = -NJ ( - : - = ~ = -0. 349 NJ,

(7)

w o r s e than the wave function eqn. (5) which is obviously v a r i a t i o n a l .

On the

o t h e r hand, it is e a s y to i m p r o v e eqn. (5) e i t h e r by p e r t u r b a t i o n t h e o r y o r by

the s i m p l e p r o c e d u r e of Hulthdn (5).

He s o l v e s for the e n e r g i e s of c h a i n s of

2, 4, 6, 8, and 10 a t o m s , u s i n g the i d e n t i t i e s
( 1 - P e m ) ( k ~ ) ( m n ) = (~fm)(nk)

(8)

where

1-

2S2Sm

and
(k~)(mn) + (kn)(~-m) + (km)(nZ) = 0.

(9)

T h e s e two i d e n t i t i e s allow one to c a l c u l a t e the effect of the H a m i l t o n i a n eqn.

(1) on any wave function of a c o n f i g u r a t i o n e x p r e s s e d in the f o r m (k2)(mn) . . .
R u m e r (7) and Pauling (8) have given r u l e s for d e t e r m i n i n g which and how
m a n y of t h e s e c o n f i g u r a t i o n s a r e independent: as we see f r o m eqn. (9), in
g e n e r a l one c o n f i g u r a t i o n (which may be e x p r e s s e d in t e r m s of a " L e w i s
bonding d i a g r a m " ) is not o r t h o g o n a l to, n o r even independent of, a n o t h e r .
T h i s m a k e s the a l g e b r a of v a l e n c e bonds quite a bit m o r e c o m p l i c a t e d than
that of s i m p l e b o s o n s or f e r m i o n s .

But, in g e n e r a l , as Pauling has shown,

c o n f i g u r a t i o n s without c r o s s e d bonds a r e at least independent.

Having c a l c u -

lated H ~ in t e r m s of bonding s t r u c t u r e s , the s e c u l a r e q u a t i o n may be set up

d i r e c t l y , as Hulth6n points out, without r e c o u r s e to an o r t h o n o r m a l function
set.

The r e s u l t s e x t r a p o l a t e w e l l to the exact a n s w e r .

T h e s e chain solutions a r e obtained by w r i t i n g the wave function a s a

l i n e a r c o m b i n a t i o n of p r o d u c t s of p a i r - b o n d wave functions of the type of eqn.

(5).

Thus, they a r e m u c h m o r e c l o s e l y r e l a t e d to eqn. (5) than to eqn. (2).

Vol. 8, No. 2

RESONATING VALENCE BONDS

157

It is, h o w e v e r , o b s e r v e d (9) that in the final g r o u n d s t a t e t h e r e is a b r a n c h of

t r i p l e t e x c i t a t i o n s with v e r y low e n e r g i e s , going l i n e a r l y to z e r o with m o m e n t u m k.

T h i s b r a n c h d o e s not a g r e e in m u l t i p l i c i t y o r e n e r g y with spin w a v e

t h e o r y , y e t is often c i t e d a s e v i d e n c e for its e s s e n t i a l c o r r e c t n e s s .

e q u a l l y [Link] i n t e r p r e t a t i o n s e x i s t within the r - v - b context.

We feel

T h i s a l l m a y be

r e l e v a n t to a c t u a l p h y s i c s in the c a s e of s o m e s y s t e m s in which c h a i n s of r e l a t i v e l y s t r o n g l y c o u p l e d spin 1/2 ions a r e w e a k l y c o u p l e d to e a c h o t h e r .

Now let u s c o n s i d e r two d i m e n s i o n s , and s p e c i f i c a l l y the t r i a n g u l a r
layer lattice.

First,

what is the N~el s t a t e ?

The b e s t one is not a s i m p l e

a n t i f e r r o m a g n e t i c ; it is o b t a i n e d by dividing the l a t t i c e into t h r e e s u b l a t t i c e s

and s e t t i n g the s p i n s of the t h r e e l a t t i c e s at 120 to e a c h o t h e r .

The e n e r g y

of t h i s s t a t e is

A
1
(EN~el) = -N J(3 x ~ x

S2

= -0. 375 NJ.

(i0)

This is the energy which is comparable with eqn. (3) and corresponds to a
wave function like eqn. (2), with each spin parallel to its local field.

This

energy may be improved as usual by estimating the decrease in spin-wave

zero point energy due to dynamic coupling of the spins.
The energy, calculated by the technique of Stern (I0), and corrected
according to Kubo (6) is roughly
(AEN6el) = (-0.463 _+0. 007)NJ.
The spin waves have convergent zero-point motion.
amplitude corresponds to S ~ 0.32.
Z

(11)
We estimate that its

Thus at absolute zero the N~el state can

be consistently postulated to be a locally stable minimum in the total energy.

What we now set out to indicate is that it is not the absolute minimum.

The

only way at present available is to estimate the actual ground-state energy and
show that lit is appreciably lower than eqn. (ii).
The t w o - d i m e n s i o n a l c a s e a l s o p e r m i t s a p a i r - b o n d t r i a l w a v e function.
In fact, t h e r e a r e an infinity of t h e m of the s a m e e n e r g y , s o m a n y a s to have
an a p p r e c i a b l e e n t r o p y , s i n c e p a i r bonds m a y be laid down on the l a t t i c e in at
least 23N/8 ways.

The e n e r g y of e a c h is the s a m e a s eqn.

(12):

158

RESONATING V A L E N C E BONDS

0)

Vol. 8, No. 2

E
= -0. 375NJ. (12)
pair-bond
It s e e m s likely that at finite

/ V V V V V V V V V V ~ S - - -

t e m p e r a t u r e s the e n t r o p y in//

Z...-V/k-"7

volved m a y often lead to a

b)

c l a s s i c a l p a i r - b o n d liquid
state; in a r a t h e r d i f f e r e n t
FIG. 1

c a s e , McWhan and Rice have

(a) The r a i l r o a d - t r e s t l e l a t t i c e ,
(b) S u c c e s s i v e a p p r o x i m a t i o n s to it with

s u g g e s t e d this p o s s i b i l i t y (11).
We, h o w e v e r , a r e looking

n = 2, 4, 6, 8, . . .

f o r g r o u n d s t a t e s in w h i c h

.50"

t h e s e m a n y d i f f e r e n t bond
_+ . 0 0 2

configurations are linearly

c o m b i n e d in the s a m e w a v e function to l o w e r the e n e r g y .
The s i m p l e s t s y s t e m

~]~

.45 -

in which m a n y d e g e n e r a t e

p a i r - b o n d s t a t e s e x i s t is a
o n e - d i m e n s i o n a l s y s t e m we
m a y c a l l the r a i l r o a d t r e s t l e
l a t t i c e (see Fig. la).
.40 -

It is a

piece of the t r i a n g u l a r l a y e r
and as such its e n e r g y is
v a r i a t i o n a l for that of the
.5

2/n

layer.

Its N6el state e n e r g y

is no b e t t e r than the l i n e a r

FIG. 2

chain, its p a i r bond e n e r g y ,

A p p r o x i m a t e e n e r g i e s for the r a i l r o a d - t r e s t l e :
s u c c e s s i v e n = 2, 4, 6, 8 e s t i m a t e s and
extrapolation.

a s a l w a y s , just (12).

We

have d e v e l o p e d a s e q u e n c e of
v a r i a t i o n a l a p p r o x i m a t i o n s to

its e n e r g y , a g a i n s i m p l y by solving a s e q u e n c e of s m a l l p i e c e s of the l a t t i c e ,

containing 2, 4, 6, and 8 a t o m s (see Fig. lb), using H u l t h d n ' s a l g e b r a i c t e c h niques.

The r e s u l t s a r e shown in Fig. 2.

The last of t h e s e e n e r g i e s is a l -

r e a d y as good as the spin wave r e s u l t , and is, of c o u r s e , v a r i a t i o n a l .

The

Vol. 8, No. 2

RESONATING V A L E N C E BONDS

159

e n e r g i e s e x t r a p o l a t e r a t h e r s m o o t h l y to
E r a i l r o a d ~ - 0 . 4 9 0 NJ + 0. 005

(13)

which should be quite a c c u r a t e and is u n m i s t a k e a b l y b e t t e r than the s p i n - w a v e

result.
A l e s s a c c u r a t e e x t r a p o l a t i o n m a y be m a d e f r o m the l i n e a r chain via
the r a i l r o a d t r e s t l e to the e n t i r e t r i a n g l e lattice.

One finds

E A ~- -(0. 54 .+. 0 . 0 1 ) N J .

(14)

T h i s is n e a r l y 20% l o w e r than the s p i n - w a v e e n e r g y (11) of the Ndel state.

s e e m s a l m o s t c e r t a i n that it
r e p r e s e n t s the e n e r g y of a
qualitatively

,r

,,

d i f f e r e n t state.

I
O~

Let us m a k e s o m e

/i
nS

,, /, , .
t

,,

,,

It

2
jr

Sw
n'

I'

ir
Ie

lit
d

SI

iv

~I

iw

Z
fS

ii w

II

iw

b r i e f c o m m e n t s about the n a t u r e
of this state.
in o r d e r :

we r e a l l y know v e r y

little about it.

hand,

A d i s c l a i m e r is
/

On the o t h e r

~kk ~k

--

there are a few very

/ /

b a s i c things w h i c h can be said.

/ ~k~k /

b) - -

/
/

/
/

We note that w h e r e v e r two

bonds a r e p a r a l l e l n e i g h b o r s ,
such as (12) and (34) in Fig.

FIG. 3

3a,

e i t h e r (S 1" S 2) or (S 3 $4) p r o vides a m a t r i x e l e m e n t to the

d e g e n e r a t e c o n f i g u r a t i o n (23)(41),

Random a r r a n g e m e n t s of p a i r bonds on a
t r i a n g l e l a t t i c e . (a) Shows a r e g u l a r a t r a n g e m e n t with 2N/4 a l t e r n a t i v e d i s t i n c t
pairings ("rhombus" approximation).
(b) An a r b i t r a r y a r r a n g e m e n t .

while only (S1S3) g i v e s a m a t r i x e l e m e n t of opposite sign.

T h u s we can a l w a y s

gain e n e r g y by l i n e a r l y c o m b i n i n g d i f f e r e n t c o n f i g u r a t i o n s in which such bonds

are interchanged.

Since t h e r e a r e in any r a n d o m c o n f i g u r a t i o n like Fig. 3b

g r e a t n u m b e r s of s e t s of p a r a l l e l bonds, one can a r r i v e at any c o n I i g u r a t i o n

f r o m any other; and r e t u r n to the o r i g i n a l one by v e r y m a n y paths.

What is

not c l e a r is that one will r e t u r n to the s a m e state in the s a m e phase by t r a v e r s i n g d i f f e r e n t paths.

If one did, the state would be e s s e n t i a l l y a B o s e con-

d e n s e d state of p a i r - b o n d s with a f o r m of ODLRO.

This would be c l o s e l y r e -

160

RESONATING VALENCE BONDS

lated to a condensation of excitonic molecules.

Vol. 8, No. 2

But this is not necessarily the

case, and only local phase coherence may be present in the ground state, as
in a Fermi rather than a Bose liquid. So in particular, it is not clear whether
one must undergo a true phase transition from a "classical pair bond liquid"
state to this state.
Next excitations: In two dimensions, it is not at all clear that the two
spins in a singlet necessarily ever separate by any appreciable distance, in
which case there may be an energy gap to the lowest triplet excitation, so that
the state need be only weakly paramagnetic if at all.

But especially if it is a

Bose state, it will probably have low-energy excitations, which may in this
case be purely singlet.

Two puzzling results to which this is relevant on TaS2

(IT) are the low paramagnetic susceptibility and the large, not quite linear,
specific heat.
I would like to acknowledge stimulating conversations at various times
with H. Ao Kramers, W. Marshall, and T. M. Rice, and discussions of their
data with D. McWhanand T. Geballe.
References
1. L. Pauling, Proc. N.A.S. 39, 551 (1953); Nature of the Chemical Bond,
p. 394. Cornell University--Press, Ithaca, New York (1960).
2. P. W. Anderson, Phys. Rev. 8_.66, 694 (1952).
3. H. W. deWijn, R. E. Walstedt, L. R. Walker and H. J. Guggenheim,
J. Appl. Phys. 4..~2, 1595 (1971).
4. W. Marshall, Proc. Roy. Soc. 232, 49, 69 (1955); H. A. Kramers,
Physica I__88, i01 (1951).
5. L. Hulth~n, Ark. Mat. Astro. Fys. 26A, # i i (1938).
6. R. Kubo, Revs. Mod. Phys. 2__55, 344 (1953).
7. G. Rumer, Nachr. d. Ges. d. Wiss. zu Gottingen, M. P. Klasse, 337
(1932).
8. L. Pauling~ J. Chem. Phys. 1, 280 (1933).
9. J. des Cloiseaux and J. J. Pearson, Phys. Rev. 128, 2131 (1962).
10. F. Stern, Phys. Rev. 9_44, 1412 (1954); also unpublished manuscript.
11o D. B. McWhan, preprint; T. M. Rice, private communication.