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showing that bonding capabilities of silylene, germylene, and the Fischer-type of complexation is stronger than the Schrock one.
stannylene are considerably lower than those of methylene.
The electronic states 7BI,corresponding to species with a formal Note Added in Proof. After this paper was submitted for
u bond, lie above the 5BI states, and the SB,-7B, splitting di- publication, we found out the work reported by Cundari and
minishes regularly down the group. With the exception of MoCHz, Gordonz8on the nature of the transition-metalsilicon double bond
the septets 7B1are first-order stationary points with an imaginary in which geometries and force constants of charged species
frequency associated with a wagging displacement of hydrogen CrM’H,+ (M’ = Si, Ge, and Sn)were also reported. The results
atoms out of the molecular plane. Full optimization of these and trends observed are in agreement with those found in the
species leads to C, structures (states 7A’) considerably distorted present work.
from planarity. This anomalous behavior of the transition met- Acknowledgment. This work was supported the Direccidn
al-metal bond increases down the group and is related to non- General de Investigacih Cientifica y Tknica of Spain, Project
classical distortions observed in the series of compounds Si2H6, NO. PB89-0561.
Ge2H,, and Sn2H6. Because of such distortion, the ground state
of the heaviest element of the series, MoSnH,, is found to be bent supplementary Material Available, Mulliken population analysis
(es, state 7A’) instead of planar (e2,, state 5B,). for all states of MoM’H, complexes are only available on request
Finally, comparison of naked MoM’H,, with their penta- from the author (1 1 tables).
carbonylated homologous (CO)5Mo=M’H,, reveals that, as far ~ ~~~~~~
as Mo-M’ bond strengths and dissociation energies are concerned, (28) Cundary, T. R.; Gordon, M. S. J . Phys. Chem. 1992, 96, 631.
Abstract: A new molecular mechanics force field, the Universal force field (UFF), is described wherein the force field parameters
are estimated using general rules based only on the element, its hybridization, and its connectivity. The force field functional
forms, parameters, and generating formulas for the full periodic table are presented.
-
of -150° and distort thermally to 180° with barriers to inversion
of 1 kcal/m01.~~In order to facilitate studies of a variety of
atomic associations, we have developed a new force field using
A. I. Mol. Cryst. Liq. Crysf. 1975, 31, 205. (u) Gcdleski, S. A,; Schleyer,
P. v. R.; Osawa, E.; Inamoto, Y.; Fujikura, Y . J . Org. Chem. 1976, 41, 2596.
(v) Fitzwater, S.; Bartell, L. S. J . Am. Chem. Soc. 1976, 98, 5107. (w) Bartell,
L. S.; Fitzwater, S. J. Chem. Phys. 1977, 67, 4168. (x) Bartell, L. S. J . Am.
general rules for estimating force field parameters based on simple Chem. SOC.1977.99.3279-82. (y) Kitaigorodskii, A. I. Chem. SOC.Reu. 7,
relations. This set of fundamental parameters is based only on 133. ( 2 ) Melberg, S.; Rasmussen, K. J . Mol. Struct. 1979, 57, 215-39. (aa)
the element, its hybridization, and connectivity. We refer to this Brooks, B. R.; Bruccoleri, R. E.; Olafson, B. D.; States, D. J.; Swaminathan,
new force field as a Universal force field (UFF). The angular S.; Karplus, M. J . Comput. Chem. 1983, 4, 187. (bb) Nilsson, L.; Karplus,
M. J . Compuf.Chem. 1986, 7, 591. (cc)Weiner, S. J.; Kollman, P. A,; Case,
distortion functional forms in UFF are chosen to be physically D. A.; Singh, U. C.; Ghio, C.; Alagona, G.; Profeta, S., Jr.; Weiner, P. J . Am.
reasonable for large amplitude displacements. The force field Chem. SOC.1984, 106, 765. (dd) Weiner, S. J.; Kollman, P. A.; Nguyen, D.
functional forms and parameters are discussed in section 11. T.; Case, D. A. J . Comput. Chem. 1986, 7, 230. (ee) Allinger, N. L. J . Am.
Results for select organic, main group inorganic, and transition Chem. SOC.1977, 99, 8127. (fr) Sprague, J. T.; Tai, J. C.; Yuh, Y.; Allinger,
N. L. J . Comput. Chem. 1987, 8, 581.
(2) Mayo, S. L.; Olafson, B. D.; Goddard, W. A,, 111J . Phys. Chem. 1990,
‘Calleo Scientific, 1300 Miramont Dr., Fort Collins, CO 80524. 94, 8897.
# Materials and Molecular Simulation Center, Beckman Institute, Cali- ( 3 ) Gajewski, J. J.; Gilbert, K. E.; McKelvey, J. In Aduances in Molecular
fornia Institute of Technology, Pasadena, CA 91 125. Modelling, Liotta, D., Ed.; JAI Press: Greenwich, CT, 1990; Vol. 2, p 65.
‘Shell Development Co., Westhollow Research Center, 3333 Hwy. Six Clark, M. C.; Cramer, R. D., 111; Van Opdenbosch, N. J . Compuf.Chem.
South, Houston, TX 77082. 1989, 982.
0002-786319211514-10024%03.00/0
I , , 0 1992 American Chemical Society
UFF, a Full Periodic Table Force Field J. Am. Chem. SOC.,Vol. 114, No. 25, 1992 10025
reference structures of the parent hydrides. Thus 0 - 3 has Bo = CHj-CH, 2.93a 2.90
104.5' from HzO, while S3 has Bo = 92.2' from HzS. Exceptions CH3-SiH3 1.7" 1.7
CH3-GeH3 1.2" 1.2
include 0-32, O R , and N-2. The bond angles for 0-32,O-R, CH3-SnH3 0.65" 0.65
and N-2 are fit to (C13Si)z0,methyl vinyl ether, and dimethyl- CH3-NH2 2.0" 2.0
diazene angles of 146O, 118.3', and 112.3', respectively. Where CH3-PH2 2.0" 2.0
structural data are unavailable, the natural angles are extrapolated CH3-AsH2 1 .5" 1.5
from the element above it in the periodic table. The remaining CH3-OH 1.1" 1 .o
elements are all assumed to have regular octahedral, tetrahedral, CH,-SH 1.3" 1.3
trigonal, or linear structures. The natural angles are collected CH3-SeH 1 .O" 1 .o
in Table I. trans HO-OH 1.1" 1.7
b. Force Constants. The angle bend force constants are gen- cis HO-OH 7.0" 6.6
trans HS-SH 6.8" 6.8
erated using a previously reported angular generalization of cis HS-SH 7.2" 7.2
Badger's r ~ 1 e s . lBasically,
~ the functional form (6) is assumed anisole 4.6b 3.6
to extend to the I and K atoms of a angle bend for polyatomics, thioanisole 1 .Ob 1.7
and the effective charges listed in Table I are used. Thus starting acetaldehyde 1.17" 0.83
with isoprene 2.7lC 1.56
ethylbenzene 1.16' 3.16
Eo = Eo - FB - @(z1*zK*/rIK)
"Lister, D. G.; Macdonald, J. N.; Owen, N. L. Internal Rotation
where F is to be determined and and Inversion; Academic Press: New York, 1978; pp 164, 165.
*Schaefer, T.; Penner, G. H. Can. J. Chem. 1988, 66, 1641.
+
rIKz = rlJZ rJKZ- 2rlJrJKcos e CCompton,D. A. C.; George, W. 0.;Maddams, W. F.J . Chem. SOC.,
taking the second derivative of E with respect to 0 yields: Perkin Trans. 2 1976, 1666. dMiller, A.; Scott, D. W. J. Chem. Phys.
1978, 68, 1317.
bridized centers X-1 were assigned a value of zero. In addition, xIJ = y2<x1 + XI) (214
when angles about the central atoms approach 180°, the potential
energy and derivative terms are set to zero as is conventionally where x I is the atomic van der Waals distance, is analogous to
done. the summing of covalent radii as used in eq 2 above for bond
The remaining exception is for the case of a single bond in- distances. Use of a geometric mean combination rule for distance
volving one sp2 atom and one sp3 atom where the sp2 atom is
bonded to another sp2 atom (e.g., propene). For this case we use xIJ = %
4 (21b)
Vo = 2.0 kcal/mol, n = 3, and do = 180O.
The overall reproduction of torsional barriers is quite good (see facilitates summation of van der Waals terms for crystalline
Table 11). The C-3-sp3 barriers were chosen to fit the experimental systems. The molecular parameters (distances, angles, inversion
barriers, the H202and H2S2values were best compromise values, barriers, and torsional barriers) are developed here using geometric
and anisole, thioanisole, acetaldehyde, isoprene, and ethylbenzene distance combination rules. UFF assumes standard geometric
are tests of eq 17. combination rules for the well depth:
3. Inversion. For UFF, a one- or two-term cosine Fourier DIj = (DIDJ)1/2 (22)
expansion in w is used for atoms I bonded exactly to three other
atoms J, K, L: where DI is the atomic van der Waals energy. Values of the van
der Waals distances xI and DI for UFF are listed in Table I.
E , = K I J K L (+ ~ OCI COS WIJKL + C2 COS ~ W I J K L )(18) The most difficult part of developing a general force field is
where K I j K L is the force constant in (kcal/mol) and w1jKL is the the assignment of van der Waals parameters. The present Len-
angle between the IL axis and the IJK plane. For a given central nard-Jones van der Waals parameters are developed within the
atom I there are three unique axes (IL, IJ, and IK); all three are conceptual framework of the exponentiald form. This functional
considered, with each inversion barrier being divided by the form is physically based on the short-range exponential repulsion
number of inversions present (three) about center I. The cos 2w arising from Pauli orthogonalization and the long-range 1/#
term yields a minimum for w = 90° and a maximum for w = O0 induced dipole-induced dipole dispersive attraction:
as would be appropriate for PH3. The cos w term yields a min- EvdW = Ae-BX- c 6 / X 6
imum for w = Oo and a maximum for w = 180° as would be (23)
appropriate for ethylene. Linear combinations of these terms will The repulsive exponential B and the dispersive attractive term
describe all intermediate cases. The inversion potential can also C, are developed below for the entire periodic table. The third
be expressed in terms of the computationally convenient normal degree of freedom contained in eq 23 is determined from an
to the IJK plane and the angle that the IL axis makes with respect empirical relation obtained between literature values of Len-
to the normal to the IJK plane, 7 I j K L . The two forms are related nard-Jones distances and the present repulsive exponentials B.
by w = y - T . The repulsion exponent B can be developed from a consideration
+ CI sin YIJKL + Cz' COS ~ Y I J K L )(19) of the physical basis of the repulsive term, that is, the repulsive
E , KIJKL(CO interaction between pairs of closed shells. This repulsive interaction
For C-2 and C R sp2 atom types with exactly three substituents, to first order is proportional to the overlap between the wave
C, = 1, Cl = -1, and C2 = 0. If carbon is bonded to 0-2, the functions squared. We begin with the approximate relationZ2that
force constant is set to 50 kcal/mol, as fit to the bz wag of the long-range distance dependence of a wave function is
formaldehyde; otherwise, the force constant is set to 6 kcal/mol,
as fit to the low-energy a,, blur and b2 vibrational modes of
ethylene and the low-energy e2,, a2,, and bzavibrational modes
e-(fir
\k - (24)
of benzene.l* Force constants for groups 5 and 6 were chosen to The overlap between a pair of exponential functions (with the same
fit the experimentally observed inversion barriers for the group Slater exponent 5 ) is
5 hydrides NH3 and PH3.21 The wo were obtained from standard S = (1 + 5r + y3(5r)2)e-€r (25)
reference structures of the hydrides and the C,, coefficients fit to
a minimum with E, = 0 at w = wo and that E , for the maximum Thus the repulsive interaction (S2)between a pair of atoms
at w = Oo be equal to Ebarricr. In order to fit observed barriers,
inversion terms corresponding to Ebarrier = 0 for nitrogen and 22
s2 e-2€r - (26)
kcal/mol for P, As, Sb, and Bi are used. The inversion force is directly related to the electron density where, from eq 24
constants for all other atom types are set to zero.
E. van der Waals. Nonbonded interactions (van der Waals 5 = d21P (27)
forces) are included in the Universal force field. A Lennard-Jones
6-1 2 type expression is used: This leads to the exponent in the exponential-6 being defined as
B = 25 = 2 d 2 I P (28)
The ionization energy for each atom I (IP,) in the entire periodic
table can be obtained from the sum of the G M P electronegativity
where DIJ is the well depth in kcal/mol and xIJis the van der and idempotential:I3
Waals bond length in A. The 6-12 Lennard-Jones form is chosen
over an exponential-6 form (discussed below) for its numerical IPI = XI +724 (29)
stability; the exponential-6 form blows up for small internuclear
separations. A complete set of exponential-6 parameters are The dispersion terms c6 are taken as proportional to the upper
provided in Table I although the valence parameterization dis- bound numerical Hartree-Fock values presented by Fraga,
cussed above actually used Lennard-Jones 6-12 nonbond poten- Karwowski, and Saxena (FKS).23
tials.
As is conventionally done, the general xIJand DIj are obtained c
6 = csFKS/s (30)
from the homonuclear parameters through the use of combination A plot of the FKS values for the noble gases versus the semi-
rules. The choice of combination rules for the Lennard-Jones empirical values reported by Kwnar and is used to obtain
distances is somewhat problematic. The use of an arithmetic mean
for the Lennard-Jones distance,
(22) Handy, N. C.; Marron, M. T.;Silverston, H. J. Phys. Reu. 1969,180,
45.
(21) Lister, D. G.; Macdonald, J. N.; Owen, N. L. Internal Rorarion and ( 2 3 ) Fraga, S.;Karwowski, J.; Saxena, K. M. S.Handbook of Atomic
Inversion; Academic Press: New York, 1978; pp 179-180. Dora; Elsevier Scientific: Amsterdam, 1976.
10030 J. Am. Chem. Soc., Vol. 114, No. 25, 1992 RappP et al.
T
1
2.1
zeta 12.)
Zeta I 13
1.9 Zeta = 14
P
s 0.2
\ '
5P O I
-0.2
-0'41
-0.6
.0.8 1
I I
I
1.1 I I
I , I , I
2 2.4 2.8 3.2 3.6 4
R (4
0 9 18 27 36 45 54
2 Figure 2. Plot of an exponential-6 van der Waals term as a function of
{ = 12, 13, and 14 with B, set to 4.3333 A-' and C,, set to 676.929
Figure 1. A plot of the Kraga, Karwowski, and Saxena c6 dispersion (kcal/mol) /A6.
terms versus the semiempirical values of Kumar and Meath. The line
is the least-squares fit. 17
-0- Second Period
X
(32)
Table IV. van der Waals Parameters
A comparison of like terms in eq 23 and 32 leads to eq 33 for the
distance, literature Universal
element ref XI DI XI DI
XI = t/BI (33)
C 15 3.898 0.095 3.851 0.105
eq 34 for the well depth N 27 3.662 0.077 3.660 0.069
0 27 3.405 0.096 3.500 0.060
F 27 3.472 0.073 3.364 0.050
(34) Ne a 3.243 0.072 3.243 0.042
P 2 4.15 0.32 4.147 0.305
S 2 4.03 0.344 4.035 0.274
and eq 35 for the repulsive preexponential term. C1 2 3.950 0.283 3.947 0.227
Ar a 3.867 0.239 3.868 0.185
As a 3.35 0.6 4.230 0.309
(35) Se b 3.70 0.517 4.205 0.291
Kr a 4.165 0.329 4.141 0.220
As discussed previously? there are three simple choices for this Sb a 3.54 0.5 4.420 0.449
third parameter r:
(1) assign a value of 12 to (, which results
Te
Xe
b
a
3.74
4.512
1.23
0.457
4.470
4.404
0.398
0.332
in the Lennard-Jones and exponential-6 forms having precisely
the same long-range distance dependence; (2) assign a value of "Fit to the elemental crystal structure, this work. bFit to the ele-
mental crystal structure, WAG unpublished results.
13.772 to (, which gives the exponential-6 and 6-12 forms the
same curvature at the bottom of the well; or (3) fit (to a discrete Using the BI defined by eqs 28 and 29 and literature valueszJ8
set of crystal structures for each element. Figure 2 shows the for exponential-6 or 6-12 xI(s, linear relations are observed for
Lennard-Jones curves for three values of (with B and c6 fixed. ( (which is BI/xI) as a function of the number of valence electrons
Given the extreme sensitivity of the resulting Lennard-Jones and row in the periodic table (see Figure 3). The scatter in the
parameters to the choice of (, the enormity of the challenge of plot for the second period can be attributed largely to the choice
fitting parameters for the entire periodic table, and the difficulty of partial charges for the molecules used in the determination of
in factoring out special intermolecular bonding interactions in the the xIparameters from X-ray crystal structures. Given the un-
crystal structures of the element^,^^*^^ we have chosen to use the certainty in partial charge assignment, we have chosen to use two
available data and empirically estimate { as discussed below. neutral cases ( = 12.73 for C, from graphiteI5 and ( = 15.44 for
(24) Kumar, A,; Meath, W. J. Mol. Phys. 1985, 54, 823. (28) Williams, D. E. Acta Cryst. 1974, A30, 71. Williams, D. E.; Starr,
(25) Spackman, M. A. J. Chem. Phys. 1986, 85, 6579. T. L.Compur. Chem. 1977,1, 173. Williams, D. E.; Hsu,L.Y.Acra Crysf.
(26) Hsu,L. Y.; Williams, D. E. Acra Crysr. 1985, A41, 296. 1980, A36, 277. Cox,S. R.; Hsu,L.Y.; Williams, D. E. Ibid. 1981, ,437,293.
(27) Desiraju, G. R.; Parthasarathy, R. J. Am. Chem. SOC.1989, 111, Williams, D. E.; Cox,S. R. Ibid. 1984, 840, 404. Williams, D. E.; Houpt,
8725. D. J. Ibid. 1986, 8 4 2 , 286.
UFF, a Full Periodic Table Force Field J. Am. Chem. SOC.,Vol. 114, No. 25, 1992 10031
Ne to obtain a linear relation, eq 36, for the second period. Table V. Optimized Alkali Lennard-Jones Parameters
( = 10.02 0.6775n+ (36) metal am; a,~d Dllb 41"
For the third period a least-squares fit to the xI data in Table IV LiF 4.026 4.026 0.05 2.298
(for the third period) leads to: NaF 4.628 4.629 0.06 2.824
KF 5.344 5.344 0.07 3.637
+
( = 8.587 0.897n (37) RbF 5.64 5.64 0.08 3.931
CsF 6.002 6.002 0.09 4.335
The discontinuity in slope between the third and fourth periods
'Angstroms. In kcal/mol.
in Figure 3 can be attributed to the onset of special intermolecular
, ~ ' S are both nonmetals
bonding interactions in the ~ o l i d s ; ~P~ and
but As and Se are both metallic or near metallic. These special radius and well depth of 3.805 A and 0.069 kcal/mol fit to gra-
bonding interactions should not be included in a van der Waals phite.I5
parameter set. Thus, for the remaining main group elements, eq F. Electrostatic hteractiom. The valence parameters discussed
38 is used wherein a slope of 1 is assumed (extrapolated from the in the above sections were obtained without partial charges. When
slopes of eq 36 and 37 and the noble gases are assigned a value included, electrostatic interactions are calculated by:
of 15. E,, 332.0637(QiQj/<Rij) (43)
(=8+n (38) Qi and Qj are charges in electron units, Ri. is the distance in
The repulsive expmentials Band dispersion terms c 6 along with angstroms, and c is the dielectric constant. Tke default dielectric
the shape parameters t are used to define the Lennard-Jones constant is 1 for UFF and no distance cutoff is used. Partial
distances xIand well depths using eq 33 and 34. charges are obtained using the recently published QEq charge
The thus obtained Lennard-Jones parameters provide reasonable equilibration scheme.30
estimates for the elements in their atomic state. A comparison C. Nonbonded Exclusions. With UFF we follow the usual
of the UFF Lennard-Jones parameters with literature values for convention of excluding van der Waals and electrostatic inter-
several elements is provided in Table IV. actions for atoms that are bonded to each other (1,2 interactions)
For metals in positive oxidation states, the above estimates are or bonded to a common atom (1,3 interactions).
not appropriate. For cationic metals we have obtained ionic c61+
and BIt as follows. The exponent BIt is defined as III. Calculational Results and Summary
Detailed comparisons of conformational energetics and mo-
(39) lecular structures with experimental and published MM2(3) results
for organic compounds3' and application of UFF to predict
where IP21is the second ionization energy for atom I as obtained structures of main transition metal inorganic, and or-
from the GMP electronegativity and idempotentiali3 ganometallic compounds33are the subjects of future papers. Here
we present the results on a select set of molecules to demonstrate
the overall utility of the approach. We begin with structural
The c61t are obtained by scaling the neutral c6, terms by the comparison for a few organic molecules where the bond order
ratio of the London estimates for the neutral and positive ion C i s varies to demonstrate the utility of a radius plus bond order
thus,
c, - IPa2 (41)
correction distance function, eq 2. This is followed by three main
group inorganic molecules: octamethylcyclotetrasiloxane,
1,3,5,7-tetrakis(trifuoromethyl)-2,4,6,8,9,lO-hexathia-l,3,5,7-
tetragermaadamantane, and dodecaphenylcyclohexastannane.We
conclude with calculations on a set of transition metal complexes
where I F I and IPI are the experimental first and second ionization including tris(hexamethyldisilylamide)scandium(III), (L- or D-
energies of atom I, and aIand are the FKS polarizabilities alanine-N-acetato)(L-histidinato)chromium(III), bis(N-allyl-
for the metallic neutral and positive ions. Setting (to 12 for the salicylidineiminato)nickel(II), and 1,2-bis(dimethylphosphino)-
metallic ions the Lennard-Jones distance, xIt can be directly ethane(neopentylidyne) (neopentylidene)(neopentyl)tungsten (VI).
obtained from eq 33 and DI+from eq 34. A procedure. Minimizations were camed out on a IRIS 4D20
These Lennard-Jones parameters provide reasonable values for using a Newton-Raphson minimization scheme with a norm of
elements in a cationic state. For example, the UFF distance and the gradient convergence criteria of 1 X (kcal/mol)/A and
well depth of x1 = 3.148 A and DI = 0.036 kcal/mol for Ag can were verified as minima by the absence of negative eigenvalues
be compared with a distance parameter of xI = 3.100 A obtained in the force constant matrix. Saddle points for torsional barriers
by fitting the crystal structure for AgCl with a QEq partial charge were obtained using a hill climbing algorithm and were verified
on Ag of 0.62 and a DI assigned a value of 0.036 kcal/mol. The by the presence of a single negative eigenvalue in the force constant
experimental cell parameter for AgCl is 5.556 A;29 if the UFF matrix.
Ag' parameters are used, a cell constant of 5.592 A is obtained. B. Organics. The C-3, (2-2, and C-1 radii as well as X of eq
For metals with one electron in the valence shell, the above 3 were chosen to reproduce the various C-C distances of propane,
procedure breaks down; the discontinuity in the IP versus charge propene, and propyne. From the results presented in Figure 4
curve associated with removing an electron from the core, rather (experimental quantities in parentheses), it is apparent that it is
than an additional valence electron, is likely responsible. For the possible to reproduce the five unique distances in the set with four
group 1 elements we have chosen to fit the distance parameters adjustable parameters (three radii plus bond order scaling pa-
to experimental lattice parameters with assumed well depths. The rameter A). Further, the experimental C-H distances in propene
results of the fits are provided in Table V. and propyne are also reproduced. The angles are less well re-
The derived van der Waals parameters can be compared to van produced: the C-C-C angles of propane and propene are un-
der Waals parameters in the literature explicitly fit to crystal derestimated by 1.1" and 2.3'. Further, the central C-C bond
properties. The present hydrogen radius and well depth of 2.886 of butadiene is long by 0.006 A, and the C-C double bonds of
A and 0.044 kcal/mol are nearly the same as the Lennard-Jones ___ ~ _ _ _ _
radius and well depth of 2.9267 A and 0.0335 kcal/mol fit to
~~ ~~
1.111
(1,096)
\
1.526
(112.4) 1.110
(1.089)
(1,091)
1 , 0 8 5 / (1.336)
F \ ( j
\ 1.111\
(1.094)
1.471
(1.345)
I 1,110
(1.090) 1.471
(1.451)
/(;:PA) p
Figure 6. Sample oxohydrocarbon structures; experimental structural
parameters in parentheses.
A short, the C-N triple bond is 0.007 A short, and the C-C single
(1.104)
bond is 0.015 A long also indicative of partial ?r bonding not
N
accounted for in the force field.
(1.482) 1.463 1 157 Reasonable agreement with experiment is also found for oxy-
(1.458) (1 157)
gen-containing organic molecules (see Figure 6). The C-0-C
angle of dimethyl ether is 2.5' smaller than experiment, though
it does open up (109.2') significantly from the equilibrium angle
of 104.51'. For methyl ethyl ether the calculated C-C distance
is 0.001 A long; the 0-methyl and 0-ethyl distances are 0.005
8, too short and 0.007 8, too long, respectively. The C - 0 4 angle
is 2.5' too small. For methyl vinyl ether the computed C-C double
bond is 0.002 A long, the C-O single bond is fit exactly, but the
-
- -
-N vinyl (2-0 distance is 0.053 8, long, indicative of partial ?r bonding
1.058 1.205 1.412 1.157 being ignored. The C-O double bond of acetaldehyde is over-
(1.058) (1.205) (1.376) (1,159)
estimated by 0.004 A, and the C-C bond is underestimated by
0.01 A. For acetone the C-C single bonds are 0.009 A short and
Figure 5. Sample nictinohydrocarbon structures; experimental structural the C-C-C an le is 2.9' large. For propynal the C-O double
parameters in parentheses. 1
bond is 0.006 long, the C-C single bond is well reproduced,
and the C-C triple bond is 0.004 A short. The calculated C-O
butadiene are calculated to be 0.015 A short. This pattern for double bond of acrolein is 0.001 A long, the C-C single bond is
butadiene indicates that partial (but not substantial) A bonding 0.002 8, long, and the C-C double bond is 0.01 A short. For
between the central carbons is not being accounted for in the force methyl formate the C-0 double bond is 0.019 A long, the ester
field. C-O single bond is 0.067 A long (indicative of missing A delo-
For nitrogen-containing organic molecules, the experimental calization), and the other C - O single bond distance is 0.012 A
structures are reasonably well described except for cases with short.
partial A bonding which is not included in this version of UFF. For amides the calculated structures are acceptable (see Figure
For dimethylamine (see Figure 5 ) , the N-H distance is 0.025 A 7). The calculated C-O double bond of acetamide is 0.002 A
too long and the C-N-C angle 1.go too small, though the angle too long, the C-C single bond is 0.021 A too short, and the C-N
has opened up significantly (1 10.2O) from the equilibrium angle resonating bond is 0.01 5 8, too short. For N-methylformamide
of N-3 (106.7'). For trimethylamine the C-N-C angle is only the calculated C-O double bond is 0.001 A short, the C-N res-
0.9' too small, though the C-N distances are 0.02 8, large. The onating bond is 0.001 A short, and the C-N single bond is fit.
C-N distance is underestimated by 0.04 A in dimethyldiazene, The C-N-C angle is 0.7' larger than experiment.
but the remaining geometric parameters are well reproduced. For For organic molecules with bonds without partial ?r bonding,
acetonitrile, the C-C single bond distance is 0.005 A long. For the force field reproduces the experimental organic structures to
2-cyano- 1-ethylene the calculated C-C single bond is overesti- within 0.02 A and 2'.
mated by 0.034 A, indicating partial A bonding between the C. Main Group. For molecules with main group-main group
centers. For 2-cyano-1-ethylene the C-C double bond is 0.005 bonds, experimental structures are reasonably well described in
UFF, a Full Periodic Table Force Field J . Am. Chem. Soc., Vol. 114, No. 25, 1992 10033
1.222
(1.220)
1I
0
Octamethylcyclotetlasiloxane
H\
1,2-Bis(dimethylphosphino)ethane- Chloromethyl-[(t)-(2S,35)-O
(necpenty1idyne)- isopropylidene-2,3-dihydroxy-
(neopentylidiene)(nepentyi)tungslen(VI) 1.4-bs(diphenyiphosphino)butane]
olatinum(lll
Figure 9. Structural formulas and numbering of atoms for a set of metal containing molecules.
amino groups trans. Overall, the experimental structure is well N-C imine distance is 0.023A long; and the N-C amine distance
reproduced by UFF. The calculated Co-N distances are in very is 0.042A short. The intrachelate N-Ni-O bond angle is 2.1°
good agreement with experiment (errors within 0.011 A). The small; the interchelate angle is 2O too large. The C, N, and 0
calculated axial Co-Cl distances are 0.012 A and 0.039 A too atoms of the salicylidineiminatoligands are described with res-
short. The calculated equatorial Co-Cl bond (trans to nitrogen) onating atom types and internal bond orders of 3 / 2 . The bonds
is 0.078 A too short, owing to an unaccounted for trans influence. to Ni use bond order 1.
The bond angles at Co are well reproduced by the force field. T r i s [ b ~ ( t r i m e t h y ~ ~ y l ) ~ ~ ~ x ~ o b iX-ray
u m ( studies
V).~
cis -Dichioro(meso -2,3-diemin0butane)paliadium(II).~~ have shown that the coordination environment of the Nb is a
Structural studies of this complex show squareplanar coordination. distorted tetrahedron, with planar nitrogen atoms. The calculated
Two chlorine atoms are in cis postions, and the diamino ligand 0-Nb-N angle is 2.6O too large. The calculated N-Nb-N angle
occupies two cis postions. The calculated results are in good to is 1.9O too small. The Nb-0 bond distance (bond order 3) is
fair agreement with the experimental structure. The calculated well-predicted. The calculated Nb-N amide bond distances are
Pd-Cl distances are only 0.003A too small. The Pd-N distances 0.005 A too long (bond order 3/2), and the calculated Si-N bond
are 0.021 A too small. The N-C distances are 0.040A too short. distances are 0.051 A too long.
The small experimental angular distortion away from strict square Methylmanganese Penta~arbonyl.4~The Mn-C distance for
planarity is underestimated by approximately 5 O with the UFF the metal-methyl bond is 0.054 A short by UFF and the Mn-C
force field. distance for the equatorial metal-carbonyl bonds are only 0.009
Bis(N-aUyEPali~yfto)~ck~(~).4~ X-ray studies have A long (bond order 2).
shown that this Schiff base complex is nearly planar. The im- trans-Bis(dimethylglyoximato)(diethyl dimethylmaionate)-
mediate coordination environment at Ni is calculated by UFF to (pyridine)cobalt.46 X-ray studies of this cobaloxime have been
be nearly planar, but significant distortions from planarity are carried out. The calculated structural parameters are in fair
observed in the next nearest neighbors. The calculated Ni-O bond agreement with the experimental results. The calculated glyox-
is 0.039 A short, and the Ni-N bond is 0.063 A short. The
computed C-O distance in the chelate ring is 0.01 1 A long; the (44) Hubert-Pfalzgraf, L.G.; Tsunoda, M.; LeBorgne, G. J . Chem. Soc.,
Dalton Trans. 1988, 533.
(45) Hellwegc, K-H. Landolt-Bornstein Numerical Data and Functional
(42) Ito, T.; Marumo, F.; Saito, Y .Acta Crystallogr., Sect. B Srrucr. Sci. Relationships in Science and Technologv; Springer Verlag: Berlin, 1976; Vol.
1971, 827, 1695. 7, p 325.
(43) Bhatia, S.C.; Bindlish, J. M.; Saini, A. R.; Jain, P. C . J . Chem. Soc., (46) Randaccio, L.; Bresciani-Pahor, N.; Orbell, J. D.; Calligaris, M.
Dalton Trans. 1980, 7, 1773. Organometallics 1985, 4, 469.
J . Am. Chem. SOC.1992,114, 10035-10046 10035
imato Co-N distances are 0.043 A long on average. The calcu- trans-influence arguments. The Pt-PI (trans to C1) is 0.007 A
lated pyridine Co-N distance is 0,119 A short, consistent with short, bond order 2. The computed Pt-P2 (trans to carbon)
a significant trans influence from the alkyl group (if a bond order distance is only 0.005 A short, bond order 1'/*. The calculated
of is used, the calculated pyridine Co-N distance is 0.047 A Pt-C and Pt-Cl distances are only 0.04 A short and long, re-
long). The Co-C distance is only 0.023 A long. spectively.
1,2-Bis(dimethylphosphino)ethane(neopentylidyne) (neo-
pentylidene)(neopentyl)hmgsten(VI).47 X-ray studies have shown IV. Conclusions
that the coordination environment of the W is a distorted square It is possible to construct a force field from simple rules and
pyramid. The experimental distortion of the square pyramid plane atomic parameters that is capable of reproducing most structural
away from tungsten is not accounted for in the present force field features across the periodic table with errors less than 0.1 A in
because an octahedral atom type is used for tungsten (W-6+6). bond distances and 5" to 10" in angle bend. Further applications
Large angular errors at W result: the UFF Cl-W-C3 angle is of UFF to organic, main group, and metal compounds are de-
too small by 8", the C1-W-C5 is too small by 20°. The ex- scribed in the following papers. Enhancements to UFF to decrease
perimental M-C single, double, and triple bond distances are well structural and energetic errors are underway.
reproduced for this unique complex. This is a remarkable result
considering a single covalent W radius is used in the U F F force Acknowledgment. A.K.R. gratefully acknowledges support of
field; the bond order correction can correctly account for the this research by Shell Development and Molecular Simulations
change in bond distance as a function of bond order. The W-C Inc. W.A.G. gratefully acknowledges support of this research
single bond is 0.05 A short, the W-C double bond is 0.027 A long, by a grant from DOE-AICD. A.K.R. and C.J.C. thank M.A.C.
and the W - C triple bond is 0.029 A long. The electronic effect for her timely arrival and Glynis Hubbard for her contributions
at metal alkylidene centers whereby the M-C-C angle is enlarged to this work.
as a result of a electronic donation from the a C-H bond to the Registry No. Octamethylcyclotetrasiloxane,556-67-2; 1,3,5,7-tetra-
metal center is not accounted for in the UFF force field, and hence kis(trifluoromethyl)-2,4,6,8,9,lO-hexathia- 1,3,5,7-tetragermaadaman-
the W-C6-C7 bond angle is 17" too small. The W-C-C angles tane, 108009-38-7; dodecaphenylcyclohexastannane, 1066-22-4; tris-
for the W - C single and triple bonds are in error by less than lo. (hexamethyldisilylamide)scandium(III), 375 12-28-0;(L- or D-alanine+
ChloromethyN(+)-(2S,3S)-O-isopropylidene-2,3-dihydroxy- acetato)(L-histidinato)chromium(II), 96126-28-2; bis(N-allyl-
l,ebi~(aipaenylp~phino)butanelplatinum).~~ The structure salicylidineiminato)nickel(II), 55292-18-7; 1,2-bis(dimethylphosphino)-
of this complex has been analyzed crystallographically and the ethane(neopentylidyne)(neopentylidene)(neopentyl)tungsten(VI),
70878-65-8.
coordination of the platinum is essentially square planar. The
two Pt-P bond distances are significantly different, consistent with Supplementary Material Available: Tables of reference com-
pounds used to obtain covalent radii for main group and transition
(47) Churchill, M. R.; Youngs, W. J. Inorg. Chem. 1979, 18, 2454. elements (8 pages). Ordering information is given on any current
(48) Payne, N. C.; Stephan,D. W. J . Organomef. Chem. 1982,228,203. masthead page.
Abstract: The application of a Universal force field (UFF) to the treatment of organic molecules is described. The ability
of the force field to predict the structures of a variety of organic molecules is examined, and the results are compared with
the MM2 or MM3 force fields. UFF correctly predicts the structures of unstrained and uncongested hydrocarbons, silanes,
alkenes, saturated amines, saturated ethers and phosphines, aromatic systems, and simple unconjugated multiple bond containing
compounds such as nitriles, ketones, and imines well. Bond angles are usually correct to within 3O, and bond lengths usually
to within 0.02A. Specifically, the rms error in the UFF predicted C-C bond distances is 0.021 A, with a maximum of 0.067
A for a set of 65 distances. For comparison, the MM2/3 RMS error in C-C distances is 0.012 A with a maximum of 0.029
for the same set of molecules. The UFF rms error in C-N bond distances is 0.024A, with a maximum of 0.041 A for a set
of 13 distances. For the same set of molecules, the MM2/3 rms error in C-N distances is 0.013 A with a maximum of 0.031.
The UFF rms error in C-O bond distances is 0.025 A, with a maximum of 0.05 A for a set of seven distances. For the same
set of molecules the MM2/3 rms error in C-0 distances is 0.007 A with a maximum of 0.015. The ability of UFF to calculate
conformational energy differences in simple organic molecules is also examined.
I. Introduction and energies; the molecular mechanics results are usually of ex-
Over the last two decades, molecular mechanics has developed perimental accuracy. However, as pointed Out in the first paper
into a powerful and standard method for studying the molecular of this series,4 standard force fields such as MM2 are limited to
structure and related properties of organic molecules. The MM2,I
MMP2: MM33 for& fields, develop& by Allinger and his group,
(1) Allinger, N. L. J . Am. Chem. SOC.1977, 99, 8127.
are the premier force fields for the prediction of organic structures (2) Sprague, J. T.; Tai, J. C.; Yuh, Y.; Allinger, N. L. J . Compuf.Chem.
1987, 8;58i.
Calleo Scientific. (3) Allinger, N. L.; Yuh, Y. H.; Lii, J.-H. J . Am. Chem. SOC.1989, 1 1 1 ,
tColorado State University. 855 1.