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On the Restricted Step Method Coupled

with the Augmented Hessian for the
Search of Stationary Points of Any
Continuous Function

JOSEP MARIA ANGLADA

C.I.D.-C.S.I.C., Jordi Girona Salgado 18-26, E-08034 Barcelona, Catalunya, Spain

JOSEP MARIA BOFILL

´
Departament de Quımica `
Organica, Universitat de Barcelona, Martı´ i Franques
` 1, E-08028 Barcelona,
Catalunya, Spain; E-mail: jmbofill@canigo.qo.ub.es

Received April 17, 1996; accepted June 5, 1996

ABSTRACT
In any optimization using the augmented Hessian technique, the step is not restricted to
any length. Since the restriction of the step at each iteration is very important in order to
achieve good convergence, we present a coupled method such that the augmented
Hessian automatically gives both the adequate length of the step and the correct Hessian
structure. The method is showed for the minima and saddle points of any order. Q 1997
John Wiley & Sons, Inc.

function is stationary at the point x if its gradient

Introduction vector at this point is the null vector gŽx. s 0. In
addition, the type of stationarity is characterized
analyzing its Hessian matrix HŽx. at this point. The

T he search of stationary points Žminima, max-

ima, and saddle points. of a continuous func-
tion of n independent variables is important in
many physical and chemical theoretical problems
because they correspond to the solution of the
problem under consideration. Let us assume the
continuous function f Žx. s f Ž x 1 , . . . , x n ., where the
n variables x T s Ž x 1 , . . . , x n . are independent. The
minimum character occurs if the HŽx. matrix has
positive curvatures in all the  x i 4 directions, and
the maximum, if they are all negative. For a saddle
point of order k, the matrix HŽx. has k negative
curvatures and the remaining Ž n y k . are all de-
fined positive.
During the last years, many powerful methods
have appeared in the literature regarding the search

International Journal of Quantum Chemistry, Vol. 62, 153]165 (1997)

Q 1997 John Wiley & Sons, Inc. CCC 0020-7608 / 97 / 020153-13
ANGLADA AND BOFILL

for stationary points of any type of multivariable will be called the augmented Hessian with re-
function. See, for instance, w 1]8x describing tech- stricted step ŽAHRS..
niques for minimum and saddle point searches.
The augmented Hessian ŽAH. method proposed
by Lengsfield w 9x seems to be one of the most Theoretical Basis of the Method
original algorithms and has been developed and
analyzed several times w 5, 10]13x . Basically, the The Newton and quasi-Newton methods con-
AH method consists of using a rational quadratic sist, at each iteration, of approximating the objec-
model approximation to the objective function f Žx. tive function f Žx. by a quadratic model function
rather than a simple quadratic model. As pointed q Žx.:
out by Culot et al. w 7x , this rational approximation
leads to conic isocontours of the objective function 1
which are not necessarily concentric. f Ž x . f q Ž x . s f Ž x 0 . q g T0 D x 0 q D x T0 H 0 D x 0
2
On the other hand, the introduction by Fletcher
w 1x of the restricted step or trust region technique 1 0 g T0 1
s f Žx 0 . q D x T0 .
in the optimization algorithms has been showed as
a very powerful tool to achieve good convergence
2
Ž1
ž /ž /
g0 H0 Dx0
Ž2.

1 1
w 5]8, 11, 14, 15x . Given a step size, D x 0 s x y x 0 , s f Žx 0 . q
a
D x T0 . H 0 D x ,
the ratio r between the variations of the true 2
Ž1
ž / 0

function f Žx. and the model function q Žx.,

where g 0 s gŽx 0 . and H 0 s HŽx 0 . and a H 0 is the
so-called AH of order n q 1. We denote by
f Žx. y f Žx 0 .
rs , Ž1.  h 0i , s 0i 4is1
n
the eigenvalues and the orthonormal
q Žx. y f Žx 0 . eigenvectors of the Hessian H 0 . In the standard
Newton and quasi-Newton procedures at each it-
is a measure of the goodness of the model function eration, step D x 0 is taken such that it makes q Žx.
for this step. The trust region is defined by those stationary, namely, ­ q Žx.r­ Ž D x 0 . i s 0 ; i, giving
step sizes, D x, for which the ratio r of Eq. Ž1. is
around 1. A step that fails to satisfy the latter D x 0 s yHy1
0 g0.
Ž3.
criterion may be due to the fact that D x is too long
andror the Hessian matrix has not the desired Rather than using the quadratic model Ž2. di-
structure. When these facts occur, one performs a rectly, one can employ the following rational func-
reduction of the step length along with an appro- tion w 5, 6, 9x :
priate modification of the Hessian matrix struc-
ture. Taking into account these considerations, two 1 a 1
D x T0 . H 0 D x
types of algorithms exist in the literature: One of
qr Ž x . s f Ž x 0 . q
2
Ž1
ž / 0
, Ž4.
them consists of a previous modification of the 1
D x T0 .
Hessian structure and, after that, the step length is
uniformly scaled if it exceeds a predetermined
Ž1
ž /
Dx0

criterion: See, for instance, w 6, 11x . In another type
of algorithms, the correction of the Hessian struc-
ture and the appropriate step length are evaluated
at the same time; no ‘‘a posteriori’’ uniform-scaled
is necessary on the final D x w 7, 8, 14x .
As far as we know, all algorithms that use the
AH method are of the first type, namely, one
computes step D x using the rational model and
after it is uniform-scaled. In this article, an AH
algorithm that belongs to the second type is pre-
sented, e.g., the correction of the Hessian structure
and the appropriate step length are simultaneously
obtained, preserving the nature of the rational ap-
proximation all the time. Hereafter, the method
which can be seen as a w 2r2x Pade ´ approximant to
q Žx. w 5x . In this case, step D x 0 is given by the
solution of the following two equations:
y1
D x 0 s y Ž H 0 y lI . g0 Ž 5a.
D x T0 g 0 s l , Ž 5b .
where I is the unit matrix. Equations Ž4. and Ž5.
are the basic equations of the AH method. In fact,
the method introduces an error of order D x T0 D x 0
in the standard Newton and quasi-Newton proce-
dures. Equations Ž5. are the stationary condition
requirements of Eq. Ž4., namely, ­ qr Žx.r­ Ž D x 0 . i s

154 VOL. 62, NO. 2

 STATIONARY POINTS OF ANY CONTINUOUS FUNCTION

0 ; i, and can be rewritten in a more compact form For any type of stationary point, let us say of
as an eigenvalue equation of dimension n q 1: order k, optimization using the restricted step
method w 1x can be formulated in its more general
a 0 g T0 v 1, i v form in the following way w 7, 8x :
H 0 vi s s l i 1,X i s l i vi , Ž 6 .
ž g0 H0 /ž / ž /
viX vi
Minimize Maximize q Ž x . < Ž D x T0, Ž k . D x 0, Ž k .
½
where viXT s Ž v 2, i , . . . , vnq1, i .. We will denote by D x 0, Ž nyk . D x 0, Žk.

 l i , vi 4is1
nq 1
the eigenvalues and the orthonormal
eigenvectors of the AH a H 0 . When Eq. Ž6. is used
rather than Eqs. Ž5., step size D x 0 is given by
1 D x T0, Ž nyk . s ŽŽ D x 0 . kq1 , . . . , Ž D x 0 . n .T and R is the
Dx0 s viX .
v 1, i
The main question of the AH method is the correct
selection of the eigenpair of Eq. Ž6. to take the
appropriated step D x 0 . In general, if the stationary
point to be reached is of order k, one should take
the eigenvector vkq 1 for Eq. Ž7.. The first k eigen-
vectors should correspond to the vectors with neg-
ative eigenvalues such that they characterize the
stationary point of order k. For more discussion
about this point, we refer to the analysis of Baner-
jee et al. w 5x and Khait et al. w 13x .
qDx T0, Ž nyk . D x 0, Ž nyk . . F R 2 , Ž8.
5
where D x T0, Ž k . s ŽŽ D x 0 . 1 , . . . , Ž D x 0 . k . T and
Ž7. radius of the trust region. The suggested solution
of the Min]Max problem of Eq. Ž8. is
y1
D x 0 s y ŽH 0 q m M. g0 Ž 9a.
D x T0 D x 0 s R 2 , Ž 9b .
where M is a diagonal matrix whose elements are
1.0 or y1.0. Note that the M matrix is diagonal
only in the space of the eigenvectors of H 0 . It
has as many y1.0 as the order of the stationary
point to be reached w 8x . The step length D x 0 is
evaluated by the iterative solution of Eqs. Ž9.. If

FIGURE 1. Schematic plot of F ( l) [Eq. (16)] as a function of l for the specific case of a saddle point of order one with
three independent variables.

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 155

ANGLADA AND BOFILL

TABLE I shift of the Hessian matrix H 0 , but also are slightly

Isomerization of oxirene to hydroxyvinylidene different. Using Eqs. Ž5., the perturbed Hessian
within C S symmetry: ŽH 0 y lI. does not warrant that it has the correct
O
H1 structure. This fact does not occur using Eqs. Ž9..
On the other hand, employing Eqs. Ž9., the length
C1 C2 of D x 0 falls automatically in the trust region. This
is not possible using Eqs. Ž5., but if D x T0 D x 0 - R 2
H2 and ŽH 0 y lI. have the correct structure, then AH
presents quadratic convergence w 5x . Taking into
Parameter Initial Final
account all these points, it would be interesting to
C1C 2 1.332 1.238 have a method that preserves the advantages of
C2O 1.392 1.472 both algorithms or, in others words, an AH that
C1H1 1.325 1.218 gives a D x 0 such that it falls in the trust region
C 2H 2 1.077 1.055 automatically. No further scaling will be neces-
C1O 1.872 1.845 sary.
H1O 1.371 1.438 To build up this new method, we define the
C1C 2 O 86.8 83.8 following Min]Max problem on the rational func-
H1C1C 2 94.9 103.6 tion qr Žx. defined in Eq. Ž4.:
H1C1C 2 O 0.0 0.0
H 2 C 2 C1H1 180.0 180.0
Minimize Maximize qr Ž x . < Ž D x T0, Ž k . D x 0, Ž k .
½
˚ angles in degrees.
Distances in A, D x 0, Ž nyk . D x 0, Žk.

qDx T0, Ž nyk . D x 0, Ž nyk . . F R 2 . 5 Ž 10.

the stationary point to be reached is of order k, the
shift m can take any value from max The suggested solution of Eq. Ž10. is
 max h10 , . . . , h 0k 4 , ymin h 0kq1 , . . . , h 0n 44 to `. In this y1
way, the perturbed Hessian, ŽH 0 q m M., has the D x 0 s y Ž H 0 y l9I q m M . g0 Ž 11a.
correct inertia and D x T0 D x 0 F R 2 . It is interesting D x T0 g 0 y m R 2 s l9 Ž 11b.
to compare the two sets of Eqs. Ž5. and Ž9.. In both
methods, m and l play the same role, namely, as a D x T0 D x 0 sR . 2 Ž 11c.

TABLE II
Behavior of the AHRS method for the isomerization of oxirene to hydroxyvinylidene.

Iteration DEa RMS gradient b Index c Rd Type e mf lX2g (w2 )1h Ratio i

0 y0.0020 0.0397 1 0.05 AHRS 1.8986 y0.0045 0.9987 0.86

1 y0.0021 0.0314 1 0.07 AHRS 0.8727 y0.0047 0.9975 0.94
2 y0.0018 0.0205 1 0.10 AHRS 0.2151 y0.0034 0.9950 0.96
3 y0.0008 0.0075 1 0.10 AH — y0.0012 0.9950 1.13
4 y0.0001 0.0017 1 0.10 AH — y0.0001 0.9996 1.13
5 0.0000 0.0003 1 0.10 AH — 0.0000 1.0000 1.03
6 0.0000 0.0000 1 0.10 AH — 0.0000 1.0000 1.00
a
Energy relative to the optimized point in au.
b
Rms gradient: (gT g / n )1/ 2 .
c
No. negative eigenvalues of the Hessian.
d
Radius of the trust region.
e
Type of step. The AHRS step (restricted augmented Hessian) corresponds to the solution of Eqs. (11) and the AH step
(augmented Hessian) to Eqs. (5). The selection depends on the magnitude ( D x TD x)1/ 2 ; if it is greater than R, the step is evaluated
using the AHRS equations; otherwise, it is evaluated from the AH equations.
f
The m parameter that satisfies Eq. (11c).
g
The selected eigenvalue. The eigenvalue is from Eq. (6) or (12) depending if the type of step is AH or AHRS, respectively.
h
The first component of the selected eigenvector. The eigenvector is from Eq. (6) or (12) depending if the type of step is AH or
AHRS, respectively.
i
Value of the ratio defined in Eq. (1).

156 VOL. 62, NO. 2

 STATIONARY POINTS OF ANY CONTINUOUS FUNCTION

TABLE III method where the parameter m has been decom-

Isomerization of ethylene to vinylidene within C S posed in an eigenvalue lXi plus a parameter called
symmetry: again m. Let us assume that we are interested in
H1
the optimization of a stationary point of order k. A
sketch of the AHRS algorithm is
C2 C1

H2 (a) Given x 0 and R 0 compute f Žx 0 ., g 0 , and

H 0 . Calculate the eigenpairs  h 0i , s 0i 4is1
n
of H 0
Parameter Initial Final and the gradient vector g 0 in the basis of
 s 0i 4is1
n
vectors, namely, z 0 s sT0 g 0 s Žs 10 < ???
C1C 2 1.266 1.247
<s n . g 0 . Determine the set of k eigenvectors
0 T
C1H1 1.393 1.428
C 2 H1 1.068 1.056
 s 0i 4is1
k
along the function to be maximized.
C1H 2 1.338 1.228 Except in the first iteration, the set  s 0i 4is1 k

H1C 2 C1 64.6 70.5 are the eigenvectors with the largest overlap
H 2 C1C 2 166.9 176.6 on the chosen eigenvectors at the previous
H 2 C1C 2 H1 180.0 180.0 iteration. Using z 0 and  h0i 4is1 n
as the diago-
˚ angles in degrees. nal Hessian, construct and solve the eigen-
Distances in A,
value Eq. Ž6. and take the eigenpair k q 1
Ž l kq 1 , vkq1 .. Compute D x 0 according to Eq.
Again, the iterative solution of Eqs. Ž11. will pro- Ž7. using the vector vkq 1. If D x T0 D x 0 ) R 02 or
vide the appropriate D x 0 . In fact, Eqs. Ž11a. and ŽH 0 y l kq1 I. have not the correct inertia,
Ž11b. are the partitioned form of the next eigen- then do the following microiterative proce-
value equation of dimension n q 1: dure:
ym R 2 g T0 w 1, i (b) Solve Eq. Ž11.c. using the Hebden procedure
a
H 0m wi s
ž g0 H0 q mM /ž /
wiX w 8, 16x . Now m goes from  max h10 y
l kq 1 , . . . , h 0k y l kq 1 4 , y m in  h 0kq 1 y
w 1, i l kq 1 , . . . , h0n y l kq144 to `.
s lXi s lXi wi ,
ž /
wiX
Ž 12.
(c) With the preceding m , z 0 and  h 0i y l kq1 4is1
as the diagonal Hessian, construct and solve
n

where wiXT s Ž w 2, i , . . . , wnq1, i .. We will denote by the eigenvalue Eq. Ž12. and take the eigen-
 lXi , wi 4is1
nq 1
the eigenvalues and the orthonormal pair Ž lXkq 1 , w kq1 .. Using Eq. Ž13. with the
eigenvectors of the AH a H 0m . If one uses Eq. Ž12. eigenvector w kq 1 , compute D x 0 . If D x T0 D x 0
rather than Eqs. Ž11a. and Ž11b., the step length s R 20 and ŽH 0 y lXkq1 I q m M. have the cor-
D x 0 is given by rect inertia, then the microiterative process
1 is ended; otherwise, go to Žb., making R 0 s
Dx0 s wiX . Ž 13. R 0r4.0.
w 1, i
(d) Compute x s x 0 q D x 0 , f Žx., and g. If the
Expressions Ž10. and Ž11. are the basis of the AHRS convergence criteria, Žg T grn.1r2 F « , is sat-
method. The AHRS can be seen as a restricted step isfied, then exit.

TABLE IV
Behavior of the AHRS method for the isomerization of acetylene to vinylidene.

Iteration DEa RMS gradient b Index c Rd Type e mf lX2g (w2 )1h Ratio i

0 y0.0006 0.0252 1 0.05 AHRS 0.9582 y0.0030 0.9986 1.02

1 y0.0002 0.0192 1 0.07 AHRS 0.4455 y0.0026 0.9975 0.93
2 0.0001 0.0129 1 0.10 AHRS 0.1283 y0.0014 0.9950 0.29
3 0.0001 0.0054 1 0.03 AHRS 0.3505 y0.0002 0.9997 1.06
4 0.0001 0.0036 1 0.04 AHRS 0.0737 0.0000 0.9994 1.05
5 0.0000 0.0010 1 0.04 AH — 0.0000 1.0000 1.05
6 0.0000 0.0000 1 0.04 AH — 0.0000 1.0000 1.00
a]i
See footnotes a]i to Table II.

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 157

ANGLADA AND BOFILL

(e) Compute q Žx. and r using Eqs. Ž2. and Ž1., where H 0D s S T0 H 0 S 0 is the diagonal matrix Hes-
respectively. Change the trust radius R ac- sian, i.e., ŽH 0D . i s h 0i , and z 0 s S T0 g 0 is the pro-
cording to the r values w 1, 7, 8x . If r F 0.75 jected gradient. Using the above a H 0m in Eq. Ž11a.
or r G 1.25, then R s R 0r2.0, but if 1.15 G r and substituting it into Eq. Ž11b. and rearranging,
G 0.85 and D x T0 D x 0 s R 02 , then R s R 0 we get
Ž2.0.1r2 ; otherwise, R s R 0 . Now if r ) 2.0
y1
or r - 0.0, then make x s x 0 , g s g 0 , f Žx. s lXj q m R 2 s z T0 Ž lXj I y Ž H 0D q m M. . z0
f Žx 0 ., and H s H 0 and compute a new D x 0
at the same point x 0 using the new radius R k Ž z 0 . 2i
and go to Ža.; otherwise, update or evaluate s Ý
a new H matrix and go to Ža.. is1 Ž lXj y Ž h0i y m . .
n Ž z 0 . 2i
The preceding algorithm is slightly different q Ý
from the one presented in w 7, 8x . Finally, we re- iskq1 Ž lXj y Ž h0i q m . .
mark that the microiterative procedure, steps Žb. ; j s 1, n q 1. Ž 15.
and Žc., are completely inexpensive from the com-
putational point of view. Now, we define the following function:
y1
F Ž l . s z T0 Ž lI y Ž H 0D q m M. . z0 . Ž 16.
Results and Discussion
Figure 1 plots the behavior of F Ž l. as function of l
ANALYSIS
for the specific case of a first-order saddle point
To perform an analysis of the AHRS method, with three independent variables. The set of the l
¨
we apply the Lowdin’s partitioning technique w 17x values of the points w l, F Ž l.x corresponding to the
to the eigenvalue Eq. Ž12.. First, we apply the crossing points between the straight line l q m R 2
following unitary transformation on a H 0m and the function defined by Eq. Ž16. are the set of
eigenvalues of Eq. Ž12.,  lXi 4is1
4
. Note that 4 s 3
1 0T ym R 2 g T0 1 0T Žnumber of independent variables. q 1. If the
ž 0 S T0 /ž g0 H0 q mM /ž /0 S0 straight line is l, namely, m s 0, the set of l
corresponding to the crossing points between this
ym R 2 z T0 line and the function defined in Eq. Ž16. for m s 0
s
ž z0 H 0D q m M / , Ž 14. are the eigenvalues of Eq. Ž6.,  l i 4is1
4
. Two impor-
tant conclusions emerge from the study of Figure

TABLE V
Behavior of the P-RFO method (Baker method) for the isomerization of acetylene to vinylidene.

Iteration DEa RMS gradient b Index c Type d lt se lmin f

0 y0.0006 0.0252 1 Scaled 0.0076 y0.0091

1 y0.0004 0.0209 1 Scaled 0.0046 y0.0062
2 y0.0001 0.0165 1 Scaled 0.0031 y0.0038
3 0.0001 0.0122 1 Scaled 0.0019 y0.0020
4 0.0001 0.0080 1 Scaled 0.0009 y0.0008
5 0.0001 0.0037 1 Not scaled 0.0002 y0.0001
6 0.0000 0.0002 1 Not scaled 0.0000 0.0000
7 0.0000 0.0001 1 Not scaled 0.0000 0.0000
a]c
See footnotes a]c to Table II.
d
A step is scaled if ( D x TD x)1/ 2 is greater than the radius of the trust region that is constant during all the process; otherwise, it is not
scaled. The value of this radius is 0.05.
e
According to the P-RFO method (Baker method), this corresponds to the lambda that maximizes the energy along the transition
vector (see [6]).
f
According to P-RFO method (Baker method), this corresponds to the lambda that minimizes the energy along all other vectors
different to the transition vector (see [6]).

158 VOL. 62, NO. 2

 STATIONARY POINTS OF ANY CONTINUOUS FUNCTION

1: Ž1. As occurs in the standard AH, the well- tionary point to be reached is in the middle of a
known Cauchy ‘‘interlace or betweenness’’ theo- flat hypersurface producing a deterioration of the
rem w 18x is satisfied. For a saddle point of order k, algorithm. As will be seen below, this problem is
it has the following form: lX1 F h10 y m F ??? lXk F greatly avoided using the AHRS algorithm.
h 0k y m F lXkq1 F h 0kq1 q m F ??? lXn F h0n q m F
lXnq 1. Ž2. We note that lX1 - l1 and lX2 - l2 , and
EXAMPLES
for the positive eigenvalues, lX3 ) l3 and lX4 ) l 4 .
Furthermore, lX2 is much closer to zero than is l 2 . In this section, we give some examples of appli-
To explain these effects in its more general form, cations of the AHRS method and its behavior.
we consider the eigenvalue Eq. Ž12., rearranging Some of the results are compared with the stan-
the Rayleigh quotient, i.e.: dard AH method, the so-called partitioned rational
function optimization, P-RFO ŽBaker method. w 5,
lXi s wiT a H 0m wi ; i s 1, n q 1. Ž 17. 6x . The applications concern the molecular geome-
nq 1
try optimization of the minima and first- and sec-
The vectors  wi 4is1 are orthonormalized. Differen-
tiating Eq. Ž17. with respect to m , we get
TABLE VI
­lXi Fragmentation of cyclopropylmethylene into
s yR 2 Ž wi . 1 q Ž wiX . MwiX
2 T
; i s 1, n q 1. ethylene and acetylene:
­m H5 0
Ž 18.
C1
Let us assume the optimization of a saddle point C2
of order k; then, for the eigenpair i s k q 1 se- 0
lected as step sizes, Eq. Ž18. takes the next value: H10
C4 C3
­lXkq 1 2D x T0, Ž k . D x 0, Ž k . H9 - - H

0
H8 H6 7
sy , Ž 19.
­m 1 q R2
Parameter Initial Final
where the facts that R s 2
D x T0, Ž k . D x 0, Ž k .
q
2 .y1 C1C 2 1.300 1.295
D x T0, Ž nyk . D x 0, Ž nyk . and Ž w kq1 .12 s 1 q R
Ž have
C3 C 2 1.909 2.017
been used. To first-order approximation, when m C 4C 2 1.583 2.017
tends to zero, then D m - 0, and from the previous C 4C 3 1.425 1.359
expression, D lXkq 1 s l kq1 y lXkq1 G 0, which im- C1H 5 1.059 1.083
plies that lXkq 1 F l kq1. See Figure 1, where, clearly, C3 H 6 1.096 1.068
lX2 F l2 . Also, <Ž w kq1 .1 < ª 1.0 since R 2 , in general, C3 H7 1.096 1.072
is small. C4 H8 1.110 1.068
For lXi corresponding to the negative eigen- C4 H9 1.110 1.072
value, ­lXir­m - 0, because the most important C 2 H10 1.101 1.063
component of wiX multiplies the negative part of C1C 2 C 3 110.9 110.6
the M matrix. Consequently, to first order if D m - C1C 2 C 4 118.2 110.6
C 2 C1H 5 154.8 119.0
0, then D lXi G 0, which implies that lXi F l i . For
C 2 C3 H 6 110.9 102.1
the transition vector, the corresponding eigenvalue C 2 C3 H7 109.3 104.0
becomes much more negative. Making the same C 2C4 H8 113.0 102.1
reasoning for lXi corresponding to a positive eigen- C 2C4 H9 111.0 104.0
value, the results are opposite, i.e., ­lXir­m ) 0, C1C 2 H10 131.2 147.8
since now the most important component of wiX C 4C 2 C1C 3 y51.5 y42.2
multiplies the positive part of the M matrix. Due C 3 C 2 C1H 5 y157.8 y159.0
to this fact, lXi G l i for D m - 0. From the latter C1C 2 C 3 H 6 4.1 20.9
results, we conclude that a H 0m has the negative C1C 2 C 3 H 7 134.9 143.5
and positive eigenvalues which are much more C1C 2 C 4 H 8 y23.5 y20.9
separated between both sets than are the a H 0 and C1C 2 C 4 H 9 y149.5 y143.5
H 5 C1C 2 H10 y21.5 0.0
H 0 matrices. This fact is important when the H 0
matrix has small eigenvalues, i.e., when the sta- ˚ angles in degrees.
Distances in A,

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 159

ANGLADA AND BOFILL

ond-order saddle points. Some of the calculations
were carried out with the AM1 w 19x semiempirical
Hamiltonian and others at the ab initio SCF level
of theory with the 3-21G basis set w 20x . The appro-
priate wave function Že.g., RHF, UHF, . . . . was
taken in each case. The Hessian matrices at the
starting geometries were computed either by nu-
merical differentiation ŽAM1. or by analytic sec-
ond-order derivatives Ž3-21G.. During the opti-
mization, the Hessian matrix was updated using
the Murtagh]Sargent]Powell formula ŽMSP. w 8,
21x except for the minima. In the case of AM1
calculations, the convergence criteria were taken
on the maximum component of D x and its rms
Ž D x TD xrn.1r2 , as well as the maximum compo-
nent of g and its rms Žg T grn.1r2 , with the values
9 ? 10y4 A,˚ 6 ? 10y4 A,
˚ 5 ? 10y1 kcalrmol A, ˚ and
y1 ˚ respectively, which are the
3 ? 10 kcalrmol A,
units used in the MOPAC program w 22x . In the
case of the ab initio calculations, the standard
convergence criteria of the GAMESS program w 23x
were used.
Isomerization of Oxirene to Hydroxyvinylidene
The transition structure for this reaction was
reported the first time by Bouma et al. w 24x at the
RHFr4-31G level of theory. To check the proposed
algorithm, we studied this reaction at the RHFr3-
21G level of theory. In Table I, we show the initial
and final geometrical parameters of the transition
state. The optimization was carried out within the
CS symmetry. Table II shows the behavior of the
present method. First, the initial geometry already
has the correct Hessian structure, i.e., a negative
eigenvalue corresponding to the appropriated
transition vector. Until iteration 2, the type of the
step is AHRS, namely, from the solution of the
Eqs. set Ž11.. This is because the initial step, evalu-
ated using the standard AH equations, exceeds the
radius that defines the trust region for this itera-
tion. From iteration 3 to the final convergence, the
standard AH method is employed, which means
that m s 0.0. On the other hand, the selected
eigenvalue l2 goes to zero smoothly. In the last
three iterations, the step is genuinely a
Newton]Raphson, Eq. Ž3.. Finally, we note that
the first component of the selected eigenvector
Žv2 .1 goes to 1 as the algorithm converges. The
latter behavior is normal in all AH methods.
Isomerization of Acetylene to Vinylidene
This reaction has been calculated at the ab initio
level by several authors Žsee Krishnan et al. w 25x
and references therein. and at the semiempirical
¨
level by Schroder and Thiel w 26x . We report here
the optimization of the corresponding transition

TABLE VII
Behavior of the AHRS method for the fragmentation of cyclopropylmethylene to ethylene and acetylene.

Iteration DEa RMS gradient b Index c Rd Type e mf lX2g (w2 )1h Ratio i

0 y0.0258 0.0225 2 0.05 AHRS 1.5603 y0.0066 0.9988 1.03

1 y0.0236 0.0164 2 0.07 AHRS 0.7916 y0.0056 0.9975 1.12
2 y0.0223 0.0119 2 0.10 AHRS 0.3860 y0.0060 0.9950 1.17
3 y0.0199 0.0088 2 0.14 AHRS 0.2235 y0.0095 0.9901 1.06
4 y0.0152 0.0081 2 0.20 AHRS 0.1564 y0.0132 0.9806 0.97
5 y0.0086 0.0066 1 0.28 AHRS 0.0747 y0.0146 0.9623 0.86
6 y0.0019 0.0038 1 0.28 AH — y0.0046 0.9576 0.49
7 y0.0007 0.0030 1 0.10 AHRS 0.0356 y0.0011 0.9950 0.85
8 y0.0002 0.0009 1 0.10 AH — y0.0002 0.9939 0.42
9 y0.0001 0.0012 1 0.04 AHRS 0.0290 y0.0002 0.9994 0.91
10 y0.0001 0.0004 1 0.04 AH — 0.0000 0.9997 1.26
11 y0.0001 0.0002 1 0.04 AH — 0.0000 0.9999 1.12
12 0.0000 0.0001 1 0.04 AH — 0.0000 1.0000 0.98
13 0.0000 0.0001 1 0.04 AH — 0.0000 1.0000 1.02
14 0.0000 0.0001 1 0.04 AH — 0.0000 1.0000 0.80
15 0.0000 0.0000 1 0.04 AH — 0.0000 1.0000 1.24
16 0.0000 0.0000 1 0.04 AH — 0.0000 1.0000 1.00
17 0.0000 0.0000 1 0.04 AH — 0.0000 1.0000 1.00
a]i
See footnotes a]i to Table II.

160 VOL. 62, NO. 2

 STATIONARY POINTS OF ANY CONTINUOUS FUNCTION

structure at the RHFr3-21G level of theory ŽTable
III.. In this example, we compare the present algo-
rithm with the P-RFO method or the Baker method
w 5, 6x as implemented in the GAMESS program
w 23x . As in the previous case, the selected eigenpair
of the eigenvalue Eq. Ž12. was Ž lX2 , w 2 .. From Ta-
bles IV and V, we conclude that both methods
have the same behavior. The restriction on the step
length is on until iteration 4. We remember that in
the P-RFO method the restriction is imposed per-
forming a uniform-scaling of the step length ob-
tained from the solution of the AH equations parti-
tioned conveniently w 5, 6x . The coincidence be-
tween both methods is because the Hessian has
the correct structure from the first iteration and the
eigenvalues of the Hessian are quite large in abso-
lute value during all the procedure. For instance,
the first two eigenvalues of the Hessian at iteration
zero are y0.174549 and 0.146265.
Fragmentation of Cyclopropylmethylene into
Ethylene and Acetylene
This reaction was calculated firstly by Schoeller
w 27x both at the semiempirical and ab initio levels
and by Shevlin and McKee w 28x at the ab initio

TABLE VIII
Behavior of the P-RFO method (Baker method) for the fragmentation of cyclopropylmethylene to ethylene
and acetylene.

Iteration DEa RMS gradient b Index c Type d lt se lmin f

0 y0.0258 0.0225 2 Scaled 0.0191 y0.0192

1 y0.0258 0.0209 2 Scaled 0.0135 y0.0216
2 y0.0252 0.0197 2 Scaled 0.0095 y0.0246
3 y0.0241 0.0186 2 Scaled 0.0066 y0.0275
4 y0.0228 0.0177 2 Scaled 0.0045 y0.0298
5 y0.0213 0.0170 1 Scaled 0.0031 y0.0308
6 y0.0196 0.0162 1 Scaled 0.0022 y0.0295
7 y0.0178 0.0154 1 Scaled 0.0015 y0.0276
8 y0.0159 0.0146 1 Scaled 0.0009 y0.0255
9 y0.0140 0.0138 1 Scaled 0.0006 y0.0230
10 y0.0121 0.0129 1 Scaled 0.0003 y0.0204
11 y0.0102 0.0119 1 Scaled 0.0001 y0.0176
12 y0.0085 0.0110 1 Scaled 0.0001 y0.0148
13 y0.0068 0.0100 1 Scaled 0.0000 y0.0121
14 y0.0053 0.0089 1 Scaled 0.0000 y0.0095
15 y0.0040 0.0078 1 Scaled 0.0000 y0.0072
16 y0.0032 0.0067 1 Scaled 0.0000 y0.0051
17 y0.0019 0.0056 1 Scaled 0.0000 y0.0034
18 y0.0012 0.0045 1 Scaled 0.0000 y0.0021
19 y0.0007 0.0035 1 Scaled 0.0000 y0.0013
20 y0.0004 0.0028 1 Scaled 0.0000 y0.0011
21 y0.0003 0.0025 1 Scaled 0.0000 y0.0005
22 y0.0001 0.0016 1 Not scaled 0.0000 y0.0001
23 y0.0001 0.0007 1 Not scaled 0.0000 0.0000
24 0.0000 0.0005 1 Not scaled 0.0000 0.0000
25 y0.0001 0.0003 1 Not scaled 0.0000 0.0000
26 0.0000 0.0003 1 Not scaled 0.0000 0.0000
27 0.0000 0.0002 1 Not scaled 0.0000 0.0000
28 0.0000 0.0002 1 Not scaled 0.0000 0.0000
29 0.0000 0.0002 1 Not scaled 0.0000 0.0000
30 0.0000 0.0001 1 Not scaled 0.0000 0.0000
31 0.0000 0.0001 1 Not scaled 0.0000 0.0000
32 0.0000 0.0001 1 Not scaled 0.0000 0.0000
33 0.0000 0.0000 1 Not scaled 0.0000 0.0000
a]c
See footnotes a]c to Table II.
d]f
See footnotes d]f to Table V.

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 161

ANGLADA AND BOFILL

TABLE IX Tables VII and VIII show the behavior of the

Glyoxal within C 2V symmetry: AHRS and P-RFO methods, respectively. While
O2 O1
the AHRS method converges within 17 iterations,
C1 C2 the P-RFO needs 33 iterations. In both methods,
H1 H2 until iteration 4, the updated Hessian presents two
negative eigenvalues. We remember that in the
Parameter Initial Final AHRS method the correction of the Hessian matrix
spectra is done evaluating the appropriate m pa-
C1C 2 1.921 1.509
rameter Žsee preceding sections.. At iterations 7
C1O 2 1.164 1.205
C1H1 1.444 1.083 and 9, the restricted step procedure ŽAHRS. is
C 2 C1O 2 144.1 123.1 again to increase a little more the value of the first
H1C1C 2 71.0 114.0 positive eigenvalue. From this iteration to the final
O 2 C1C 2 O1 0.0 0.0 convergence, the step is of the Newton]Raphson
H1C1C 2 O 2 180.0 180.0 type w Eq. Ž3.x . The last points are absent in the
˚ angles in degrees.
Distances in A, P-RFO method, which explains the large number
of iterations that the method needs to achieve the
convergence. This example shows clearly the im-
portance of the improvements that are associated
level only. Here, we report the results at the
to the AHRS method with respect to the standard
RHFr3-21G level of theory. In Table VI, we show
AH methods such as the P-RFO.
the initial and final geometrical parameters of the
transition structure associated to this reaction. The
final transition structure has CS symmetry while Optimization of the Glyoxal
the initial geometry has C1 symmetry. This transi-
tion state corresponds to that labeled TS1a-5 in In this subsection, we present a simple opti-
w 28x . The analysis of the Hessian spectra at the mization of the glyoxal molecule ŽTable IX.. The
initial molecular geometry presents two negative optimization was carried out at the RHFr3-21G
eigenvalues quite small in absolute value, namely, level of theory. The initial geometry was taken
y0.092790 and y0.008901. The first one corre- from the conveniently distorted transition struc-
sponds to the correct transition vector. ture of the reaction H 2 q 2CO to give glyoxal,

TABLE X
Behavior of the AHRS method for the minimization of glyoxal molecular structure.

Iteration DEa RMS gradient b Index c Rd Type e mf lX1g (w1)1h Ratio i

0 y0.1274 0.2644 1 0.05 AHRS 1.1604 y0.0073 0.9988 0.92

1 y0.1241 0.0142 1 0.10 AHRS 0.4780 y0.0078 0.9950 1.05
2 y0.1199 0.0159 1 0.20 AHRS 0.5010 y0.0302 0.9806 0.94
3 y0.1052 0.0261 1 0.40 AHRS 0.3497 y0.0920 0.9285 0.73
4 y0.0661 0.0289 1 0.40 AHRS 3.0674 y0.0374 0.9950 0.28
5 y0.0608 0.0296 0 0.10 AHRS 0.9857 y0.0201 0.9950 0.97
6 y0.0509 0.0273 0 0.20 AHRS 0.3901 y0.0343 0.9806 0.96
7 y0.0338 0.0225 0 0.40 AHRS 0.0861 y0.0447 0.9285 0.89
8 y0.0106 0.0142 0 0.40 AH — y0.0300 0.7877 y4.46
9 y0.0106 0.0142 0 0.20 AHRS 0.1568 y0.0154 0.9806 0.64
10 y0.0055 0.0155 0 0.20 AHRS 0.1738 y0.0163 0.9806 0.48
11 y0.0014 0.0081 0 0.20 AH — y0.0016 0.9963 0.67
12 y0.0009 0.0076 0 0.20 AH — y0.0025 0.9906 0.10
13 y0.0008 0.0068 0 0.05 AHRS 0.0730 y0.0012 0.9988 1.10
14 y0.0001 0.0018 0 0.05 AH — y0.0002 0.9996 0.89
15 0.0000 0.0002 0 0.05 AH — 0.0000 1.0000 0.98
a]i
See footnotes a]i to Table II.

162 VOL. 62, NO. 2

 STATIONARY POINTS OF ANY CONTINUOUS FUNCTION

TABLE XI
Behavior of the P-RFO method (Baker method) for the minimization of glyoxal molecular structure.

Iteration DEa RMS gradient b Index c Type d lmine

0 y0.1274 0.0264 1 Scaled y0.0260

1 y0.1255 0.0235 1 Scaled y0.0309
2 y0.1234 0.0162 0 Scaled y0.0062
3 y0.1223 0.0139 0 Scaled y0.0077
4 y0.1211 0.0133 0 Scaled y0.0227
5 y0.1198 0.0135 1 Scaled y0.0271
6 y0.1180 0.0180 1 Scaled y0.0558
7 y0.1149 0.0192 1 Scaled y0.0544
8 y0.1117 0.0220 1 Scaled y0.0719
9 y0.1078 0.0236 1 Scaled y0.0744
10 y0.1037 0.0253 1 Scaled y0.0844
11 y0.0993 0.0264 1 Scaled y0.0861
12 y0.0948 0.0272 1 Scaled y0.0904
13 y0.0900 0.0276 1 Scaled y0.0930
14 y0.0853 0.0277 1 — —
a]c
See footnotes a]c to Table II.
d
See footnote d to Table V.
e
According to the P-RFO method (Baker method) this corresponds to the lambda that minimizes the energy along the all vectors
(see [6]).

reported by Osamura et al. w 29x . In this case, the tion. The selected eigenpair of Eq. Ž12. for this case
updated Hessian formula used was the was Ž lX1 , w 1 .. Tables X and XI show the behavior of
Broyden]Fletcher]Goldfarb]Shanno ŽBFGS. w 1, both AHRS and P-RFO methods. While the AHRS
30x . The Hessian associated to the initial geometry achieves the correct structure of the Hessian at
still presents a negative eigenvalue corresponding iteration 5, in the P-RFO method, it is achieved at
to the transition eigenvector of the mentioned reac- iteration 2, but it loses again the correct structure
at iteration 5. This method never recovers the
correct spectra of the Hessian matrix. At iterations
TABLE XII 9, 10, and 13, the AHRS is on because some posi-
Disrotatory electrocyclic isomerization of tive eigenvalues of the Hessian updated matrix are
cyclobutene to cis-butadiene: small. Using the AHRS algorithm, the procedure
H9 H 10 converges in 15 iterations. On the other hand, the
C2 C3 H8 P-RFO never decreases the rms gradient, and at
-

H6 iteration 14, the algorithm was unable to compute

C4
-

C1 the lmin parameter. Due to this fact, the P-RFO

0

H7
0

H5 algorithm does not converge for this system.

Parameter Initial Final
Disrotatory Electrocyclic Isomerization of
C1C 2 1.479 1.433 Cyclobutene to cis-Butadiene: An Example
C 2 C3 1.299 1.343 of Localization of Saddle Point of Order Two
C1H 5 1.092 1.091
C 2H9 1.084 1.107 This section shows how powerful the algorithm
C1C 2 C 3 117.0 125.8 is in locating a saddle point of order two. For this
C 2 C1H 5 118.9 120.5 purpose, we calculated the cyclization of butadi-
C3 C 2H 9 131.9 119.9 ene into cyclobutene. In this reaction, the number
C1C 2 C 3 C 4 5.0 0.0 of p electrons determines whether the methylene
C 3 C 2 C1H 5 107.6 90.0
groups bonded to the termini of the final diene
C1C 3 C 2 H 9 180.0 180.0
system will rotate in the same direction Žconrota-
˚ angles in degrees.
Distances in A, tory process. or in the opposite direction Ždisrota-

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 163

ANGLADA AND BOFILL

tory process.. Breulet and Schaefer w 31x carried out
ab initio calculations on this reaction. According to
their conclusions, no disrotatory reaction path ex-
ists on the singlet ground-state potential energy
hypersurface connecting the cis-butadiene with cy-
clobutene. For the disrotatory motion, they found
a stationary point such that the associated Hessian
has two negative eigenvalues, namely, it is a sad-
dle point of order two in the hypersurface of 24
internal nuclear degrees of freedom. The two
imaginary vibrational frequencies correspond to
the terminal methylene twist motion, but one of
them is in phase Žconrotatory. and the other is out
of phase Ždisrotatory.. Both frequencies are sym-
metry breaking. The molecular geometry of the
saddle point of order two reported by Breulet and
Schaefer w 31x has CS symmetry but very close to
C2V symmetry Žsee Fig. 2 of w 31x. .
We studied the disrotatory path using the
UHFrAM1 method w 19, 22x and the AHRS algo-
rithm for locating the saddle point of order two.
The selected eigenpair of the eigenvalue Eq. Ž12.
was Ž lX3 , w 3 .. In Table XII, we present the initial
and final geometrical parameters. The initial ge-
ometry has C1 symmetry and the analysis of the
Hessian matrix shows one negative eigenvalue
Žy2.37794.. The final geometry has C2V symmetry
and the corresponding Hessian matrix has two
negative eigenvalues Žy0.03264, y0.03045.. The
eigenvectors associated to the negative eigenval-
ues have b 2 and a 2 symmetry and correspond to
the disrotatory and conrotatory motion of the ter-
minal methylenes, respectively.
In Table XIII, we show the behavior of the
AHRS method. The algorithm converges in 15 iter-
ations. The correct structure of the Hessian was
achieved just at the second iteration. The MSP
formula w 8, 21x was used to update the Hessian
matrix. The initial radius of the trust region Ž R .
was 0.03 rather than 0.05 and was forced not ex-
ceed the value 0.1. During all the processes, the
restricted step was used ŽAHRS.. At iterations 12
in 15, the parameter m was smaller than
max max h10 y l3 , h02 y l 34 , ymin h 03 y l3 , . . . , h 024
y l 344 . This means that the perturbed Hessian
ŽH 0 y lX3 I q m M. has not the correct structure.
One way to solve this situation consists in reduc-
ing R and evaluating again the m parameter w 8x ,
achieving a correct structure of the perturbed Hes-
sian. All these facts are due to a little more diffi-
culty to preserve a Hessian matrix of index 2 than
one of index 1 or 0. The other parameters, i.e., l3
Žselected eigenvalue., Žv3 .1 Žfirst component of se-
lected eigenvector. and the ratio, present the same
behavior as that of the previous examples.
Summary and Conclusions
We presented a modification of the standard
AH optimization algorithms such that automati-
cally the step length falls in the predicted trust

TABLE XIII
Behavior of the AHRS method for the disrotatory electrocyclic isomerization of cyclobutene to cis-butadiene.

Iteration DEa RMS gradient b Index c Rd Type e mf lX3g (w3 )1h Ratio i

0 y12.9979 17.8873 1 0.03 AHRS 1781.2 y4.1150 0.9996 1.01

1 y10.9284 11.1304 2 0.04 AHRS 799.3 y3.5171 0.9991 1.01
2 y9.1499 7.1274 2 0.06 AHRS 436.6 y3.5344 0.9982 1.01
3 y7.3626 5.4795 2 0.08 AHRS 250.9 y4.0544 0.9964 1.00
4 y5.3144 4.4673 2 0.10 AHRS 164.2 y3.8151 0.9950 1.00
5 y3.3892 3.4332 2 0.10 AHRS 117.6 y2.8486 0.9950 1.00
6 y1.9503 2.4658 2 0.10 AHRS 76.1 y1.9592 0.9950 1.00
7 y0.9560 1.6244 2 0.10 AHRS 42.0 y1.2035 0.9950 1.01
8 y0.3417 0.9348 2 0.10 AHRS 13.6 y0.5795 0.9950 1.02
9 y0.0442 0.3781 2 0.03 AHRS 33.0 y0.0615 0.9997 1.01
10 y0.0131 0.1768 2 0.01 AHRS 69.0 y0.0129 1.0000 1.00
11 y0.0066 0.1243 2 0.01 AHRS 20.9 y0.0108 0.9999 1.00
12 y0.0013 0.0543 2 0.002 AHRS 32.2 y0.0018 1.0000 1.00
13 y0.0004 0.0294 2 0.002 AHRS 65.0 y0.0004 1.0000 1.00
14 y0.0002 0.0207 2 0.002 AHRS 20.8 y0.0003 1.0000 1.00
15 0.0000 0.0097 2 0.001 AHRS 35.2 y0.0001 1.0000 1.00
a]i
See footnotes a]i to Table II.

164 VOL. 62, NO. 2

 STATIONARY POINTS OF ANY CONTINUOUS FUNCTION
region and the spectra of the Hessian is preserved.
The examples presented show that both the AHRS
and P-RFO ŽBaker method. methods have the same
behavior if the Hessian is well defined; otherwise,
the AHRS method is very powerful. Finally, we
presented an example of location of a saddle point
of order two. The main conclusion is that in this
case one has to be more restrictive in the radius
defining the predicted trust region.
ACKNOWLEDGMENTS
This research was supported by the Spanish
DGICYT ŽGrant PB92-0796-C01-02.. We are in-
debted to Professor S. Olivella for his valuable
suggestions.
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