Volume 70, number 2 CHEMICAL PHYSICS LE’ITERS 1 MaIch 1980

GEOMETRY CH’TIMIZATION IN AB INITIO SCF CAJXULATLONS.

THEHYDRffiENCtUSTERS11;:(tz=7,9,11,13)

Hanspeter HUBER
PhyMaiisch-Chemzsches Institut der Universitat Basel, CH4056 Basel, Switzerland

Received 12 January 1979; m foal form 13 December 1979

In view of the hmited accuracy and of the discrepancies between the few expenmenta! AU* values For the reactions
wn+ H2-+pn+2 (n = 1,3,5,7,9) It seemed desirable, to obtam theoretical values of -chemical” accuracy. The application
of the floatmg orbltal geometry optmuzatlon, with large basis sets, descrbed in a previous paper, yielded dissociation
energies De of 15.9,13.0 and 3.8 kJ/mol for ti7, I$ and ql, respectively. III agreement with the experimental aHo val-
ues observed by Huaoka and Kebarle, i.e. -17.2, -15.9 and -10 0 kJ/mol. A previous point by point geometry optimized
SCF calculatron on H: was reinvestrgated using a variable metric method. We obtamed an energy lower by nearly 2 kcr/mo&
This shows the superiority of gradrent methods over conventronal geometry optimization%

1_ introduction In the work reported here, we applied faster pro-

cedures for geometry optunization (variable metric
Whereas the g xon has been known to mass spec- procedure), the analytical gradient [14] and the float-
troscopists smce 1912 [ 11, q was first reported in mg orbital geometry optimization (FOGO) described
1962 [2 1. Finally, III 1969, the Hz ion clusters with in a previous paper [ 15 ] _ These methods made it pos-
7 < fz (odd) < 99 were detected [3]. Therefore, equi- sible to use larger basis sets and to optimize complete-
hbrium constants and reactlon enthalples for the reac- ly ail geometries with three exceptions. ln the latter
tions nevertheless the optimization would not change the
result significantly_ The theoretical results so obtained
%+H2-%+2 (1) are of similar accuracy as the experimental ones.
were measured only recently [4-71. To our knowl-
edge no further experimental data are avdable on
these ions. However, many theoretical calculations 2. Method and basis sets
were reported on the ions I$ and @, some of them
on a sophisticated level, yielding results of chemical A program utizing gaussian lobe functions was
accuracy (see refs. [S ,9] and references therein). In adapted for the analytical calculation of the energy
contrast, only few calculations pe avaiIabIe for the gradient and the Hellmann-Feynman force. Details
larger Ion clusters [IO-121. The older calculations of the calculations were previously reported for the
[IO, 1 l] are rather quahtative because limited basis FOG0 method [IS] and the standard procedure [14j.
sets and only partial geometry optirmzation were m- An extended search for adequate basis sets was
volved. Yamabe et al. [12] *carried out a full geom- performed on H$ and H$ taking the very accurate
etry optimization on the ions l$ (n = 3,5,7,9,11) calculations of Dykstra et al. [9] for I@ and Ahldchs
applying a 4-3 1G [13] basis set and optimized the [S] for H$ as references.
geometry partially using an extended (4-31G + gaus- Finally we decided to use the following four basis
Sian p) basis set. sets for the larger ions:
(I) Dunning’s [ 161 double zeta basis set with a
* This paper was pubhshed when our work was m progress. scaling factor of 1.2.

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Volume 70, number 2 CHEMICAL PHYSICS LETTERS 1 March 1980

Table 1 .
Energy and structure of H’s for dtiferent bass sets

Basis set E(Eh) R (a01 De UcJlmol)

(0 -127878 1631 399

(Ilr) -129337 1637 428 Frg 1. Geometry parameters for H: (CZV)-

(111) -1 29684 1640 435

(nr) -129656 1.660 434 different geometry. Our values are gtven as “Ahl. opt.”
at the end of table 2. We thmk this example demon-
(II) as (I), but used with the FOG0 method. strates the advantage of the gradient methods for ac-
(III) as (I), but wrth a polarizatron fun&on (gaus- curate caIcuIations. Compared to an electron correta-
sian p, exponent 09) tion energy of 9.6 kJ/mol the amount of 2 kJ/mol is
(LV) as (I), but extended by a gaussran sorbrtal not negligible and It seems probable that AhInchs’
with exponent 0.07 and a p-orbital with exponent CEPA result could be improved by a full geometry
0.5 and appiying the FOG0 method. Small exponents optrmization.
were chosen to account for the weak bonds in the A pecuhar rest& was found for Hz wrth a STOSG
larger ions. basis set 1133. In contrast to ah SCF cafculations
Frrst, all geometries were optm-uzed with basis (I)_ known to date it yrelds a D= geometry sirmlar to the
Wrth this basis set the calculations for most ions were CEPA calculation of Ahlnchs and a dissociation ener-
repeated with different starting geometries, to make gy of 23 0 kJ/mol. We must assume this findmg to be
sure, that the lowest mmrmum of the energy hyper- accidental as al3 other calculations on Hi clusters wrth
surface was found. As an extreme case the I$ ion was this basis set are very bad.
started as a slightly drstorted tngonai brpyramid and Basrs set (IV) performs slightly worse than (HI) for
ended m the expected C2, geometry_ The geometry Hz. This is not very surprising as there are no weak
of the lowest mmunum with basis set (I) was usually forces to account for, and the exponent of 0.5 used
used as starting geometry for the other basrs sets. in basis set (IV) may be worse than 0.9 [basis set (III)]
Table 1 summarizes the results for the H: ion, E be- in this case. For the larger rons we expect basis (IV) to
ing the energy, R the H-H drstance and De the drsso- yield De values of similar accuracy as Ahh-ichs basis set
cratron energy E(H2) - E(Hf) Table 2 shows the would grve, whereas the energres E might be worse be-
corresponding results for Hz, the geometricai param- cause there is no function with a Iarge exponent to
eters bemg defined in fig. 1. account for the cusp at the nucleus.
In addition table 2 shows the values given by
Ahhrchs [8] for the SCF calculatron. He opthmzed
the geometry with a point by pomt method. We re- 3. Energies for the ion clustersHf ,g, 61 and H&
peated the calculation with the gradient method and
found a mimmum nearly 2 kJfmo1 lower at a slightfy Table 3 shows the energres for the ion clusters Hf,

Table 2
Energy and structure of Hg for drfferent basis sets

Bans set N%) R 1h3) R2 MO) R3bo) R4 (a01 De ~J~mO~)

% -2.41026
-2.42938 1.596
I.590 1407
1.406 1.465
1.464 3.32
3.35 14.8
12.3
(Iui) -2.43560 1.560 1417 1.550 2 81 20.1
(N) -2 43698 1 579 1424 1559 2.88 24.4
bmk.hs 181 al -2 44012 1650 1410 1.486 2.95 21.3
AN opt. a) -2 44086 1573 1.416 1523 2 98 23.2
a) See tevt

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Volume 70, number 2 CHEMICAL PHYSICS LElTERS 1 &rch 1980

Table 3
Energies for the ions H?!. H$, q1 and q3

Ion Basis set E(Eh) De Wlmol) AHo W/mo9, TW).

experimental experimental

G ref. [12] -3.53521 8.8

(r) -3.54093 10.1
(10 -3 56451 12.5
ref. [12] -3.56839 13.1
WI -3.57146 12.5
0 -3.57412 15.8 -17.2 [4) 158 141
-7.5 [6J
H’g ref. 1121 -4.66506 7.9
:: -4.69913
-4.67117 11.1
9.0

ref. [12] 4.70399 11.3

WI) 4.70677 11.0
uw 4.71021 13.1 -15.9 [4] 140

G1 ref. [12] -5.79250 1.6

:; -5.83053
-5.79852 2.7
1.4

ref. [12] -5.83595 1.8

:$a, -5.84278
-5 83884 2.5
38 -10.0 [4] 108
G3 (0 -6.92580 1.3
WI -6.96192 2.6
UlI) a) -6.97093 2.6
(rv) a) -6.975 14 3.3

a) Without geometry optnnization, see text.

4, Hfl and $3 obtained wrth different baas sets.
The &ssoclation energies and the experimental enthal-
pies for the processes
H;+Hz +%+2 (n = 5,7,9)
at the temperature Tare also listed.
Bennett and Field [6] @ve a limit of error for their
experimental M” of 0.4 kJ/mol, which represents
the deviation from the average of their two measure-
ments. Comparrson with the result of Huaoka and
Kebarle [4], who give no error limrts, shows that
there must be a considerable systematrc error. Since
the experimental results for $ deviate by about 10
kJ/mol, one may assume that the experiments are not
more accurate than ~5 kJ/mol. The accuracy of the
calculatrons is hrmted by the SCF procedure and the
use of a limited basis set. The error due to the SCF
procedure may be estrmated from Ahhichs’ result [S]
for q. He obtained an eiectron correlation energy of
9.6 kJ/mol. As the bonds formed in the larger ions are
much weaker, we guess that the electron correlation
part of the dissociation energy is less than 5 kJ/mol
for $ and HG and even smaller for the larger ions.
The error due to the hmited basis set may be estimated
by comparing the results for the different basis sets_
For basis set (IV) it should not exceed 5 kJ/mol,
yieldmg a hmit for the total error of 10 kJ/mol. For
H; and $ the results are probably more accurate,
whereas for ql and q3 an even more diffuse basis
set may be necessary.
For H; (fig. 2) and H$ (fig. 3) the geometries were
optimrzed with all basis sets, there are three exceptions
for the larger ions however (see tabIe 3). The calcula-
tions with the smaller basis sets showed that the geom-
etries of Hf, and Hf in each basis set, respectively,
were a superposition of H$ and one or two H2 mole-
cules situated about 16 a0 above or below the plane of
the H3center. Therefore for the larger basis sets the
calculations were done at a fuced geometry only. That
this was a reason&le approximation is further con-
Volume 70. number 2 CHEMICAL PHYSICS LETTERS 1 March 1980

firmed by the nearly Identical dlssoclatlon energes

for Hf3 with basis set (II) (optunized geometry) and
basis set (III) (fried geometry) in accordance wth the
results for the smaller ions. In tlus context one may
note, that we found in the previous paper for Hl, that
the FOG0 method pves with a double-zeta basis a
sundar energy as a conventional calculation with a
double-zeta + p basis set. The structure, however, is
found only to be smular m these two methods usmg
the same basis set. This observation IS confirmed m
tb work for the larger Ions [compare bases (II) and
(IlI)l -
Table 3 also gves the values of Yamabe et al [12],
which were obtained Lvlth a 4-31G and 4-31G + p ba-
sis set, respectively. In order to obtam comparable
AH0 values from the calculations one has to evaluate
the followmg equation for each reactlon at the expen-
mental temperature (see table 3).
No(T) = -De + A&,(T)
+ W%,,(Tj+~~,U-)+~~l-
The difficulties m evaluating eq. (2) were pomted out
by AhInchs [8] for Hz. In contrast to Hg it may be a
good approxlmatlon for the larger ions to assume
that the or@nal vlbratlons of I-$ and H2 are hardly
changed when Hi+2 IS Formed. Then only the vlbra-
tions due to the new bonds must be taken mto account.
These bonds are however weak enough that here again
the harmonic approxuratlon IS mvahd. Therefore a
rigorous treatment of eq. (2) 1s not feasible_ We tned
to obtain a rough estimate of how much De deviates
from No(T). Treating the new mternal degrees of
freedom as free internal rotations or very low fre-
quency vibrations, we obtained m each case a probable
devlatlon of the order of RT, I e. of less than 1.5 kJ/
mol. This is only a fraction of the estimated accuracy
of our calculations (about 10 kJ/mol). Therefore we
tlunk it reasonable to compare the dissociation ener-
@es m table 3 directly wth the measured reactlon
enthalpies.
From the results one may predict the AH0 for Hfl
+H2-+Hf3 to be close to the value for Hc + H2 + Hi1
Fig 2 Geometry parameters for w, (Czv).
found that the tnangular Ion H; serves as a nucleating
center for H2 in these clusters. Agam for the larger
Ions Hfl and Hf3 one may descnbe the HG (fig. 3) as
a nucleating center. The calculations showed, that in
these cases the geometry of the I$ and the HZ, re-
spectively, is hardly changed, whereas for the smaller
ions the size of the HS triangle is affected by the addl-
tlonal H2 molecules.
Table 4 gves the size of the parameters defmed in
fig 2 for I-I; and in fig. 3 for H$. The strong basis set
dependence suggests that the potentials are very flat
and the accuracy of the geometries obtamed should
(2) not be overestimated. The geometry optirmzatlon IS,
however, important to obtam the accurate energes
Dven in the previous section.
In Hf the Hf tnangle is only slightly distorted.
Two H2 molecules are arranged perpendicularly to
the $ plane about 3.2 to 3.5 a0 off the tips of the
tnangle. Due to the very flat potential the distance
between the Hi center and the H2 depends acutely
on the basis set, and a comparison with the caIcuIa-
tions on Hg by Ahlnchs [S] suggests that m H$ too,
electron correIation has to be included to obtam this
distance accurately. The H2 bond is about 0.01 a0
longer than m Hz. Another structure with Czv sym-
metry, where one H2 molecule 1s near a tip and the

4. Geometry of the ion clusters HS , HG, $, and Hf3

In agreement with previous arguments [ 111, we Fig. 3. Geometry para;neters for wg (&h).

356
Volume 70, number 2 CHJXM[CAL PHYSICS LFTTERS 1 March t%?o

Table 4
Structures of H?, and Wg

iOn Basis set Rz(Qo) R2 (a0) R3 (a01 R4 fao) Q (de&

I.622 1.680 3.50 1.404 149

1.626 1.679 3.50 1.406 149
1.632 1.725 3.18 1.409 147
1.647 1.746 3.20 1.415 147
1.640 361 1.402
1.642 3.61 1.405
1.656 3.37 1.406
1.675 3.39 1.412

second one near the nuddle of the opposite side, both

perpendrcular to the Hf plane, is also stable with re-
spect to H2 and Hg , but IS by about 6 kJ/mol less Ill JJ.~o~n,~~.M~. 24<1912)209.
favorable [basis set (I)] than the structure given in [ 21 P H. Dawson and A.W. Tickrter, JI.Cfiem. Phys. 37
(1962) 672.
fig. I.
[31 R. Uampitt and L. Cowland, Nature 223 (1969) SLS.
In HG the optunized geometry shows D3b symme- [4] K. Huaoka and P. Kebarle. J. Chem Phys. 62 (1975)
try; the sides of the I-I$ triangle being only about 2267.
0.01 a0 longer than Hz. As no drstortion is possible [51: U A. Anfov, S L. Pozharov, LG. Chernov and ZAA.
due to symmetry, the H2 molecules are forced further Mukhamedrev, High Energy Qlem S (1971) 69,79.
f6] S-L. Bennett and F.H. Fierd, J. Am. Chem. 5%~. 94
away from the center than m E$.
t 1972) 8669.
In ql and Hf3 the geometries of H$ and H2 were (71 R. Johnsen, CM. Huang and MA. Biond& 1. C&em
hardly changed, as mentioned above. The optimal dis- phys. 65 (1976) 1539.
tance between H2 and HG IS 5.5 to 6 no_ For basis set [ 81 R. Ahlrichs. Theoret. Chim. Acta 39 11975) 149.
(I) the energy drd not change by more than 0.17 kJ/ [91 C E. Dykstra, A S. Gaylord, W.D. &I%& w-C_ iwope
and H_FF.Schaefer FII, J. Chem. Phys, 68 (1978) 3951.
no1 between 5.5 and 6.5 fro. This corresponds to a vi-
J. Easterfield and J.W. Linnett, Chem ~~~~
bration mth 7 of the order of 100 cm-f. The rotation 0970) 64.
of the H2 seems to be free in all dlrectrons. Even if the SW. Harrison,, LJ. Massa and P. Soiomoo, Nature
H2-axis stands perpendrcularly vertical to the Hf plane, Phys. SCL 245 (1973) 32.
the energy IS less than 0.1 kJ/mol brgher than if rt is S. Yamabe, K. Hvao and K. Kitaura, Chem Phys_
Letters 56 (1978) 546.
parallel.
WJ. Hehre, R-F. Stewart and JA Fople, J_ Chem.
phys. 51<1969) 2657.
H. Huber, 3. Pancd and P. &&sky, Collectron Czech.
Acknowledgement Chem. Commun. 42 (1977) 2767, sod references t&r+
in.
Financial support by Cuba-Geigy SA, Sandoz SA H. Huber, Chem. Phys Letters 62 (1979) 95.
T.H. Dunning, J. Chem. Phys. 53 (1970) 2823.
and F. Hoffmann-La Roche & Cie. SA Base1 is grate-
fully acknowledged.

357