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We report here an approach for predicting charge distributions in molecules for use in molecular dynamics simulations. The
input data are experimental atomic ionization potentials, electron affinities, and atomic radii. An atomic chemical potential
is constructed by using these quantities plus shielded electrostatic interactions between all charges. Requiring equal chemical
potentials leads to equilibrium charges that depend upon geometry. This charge equilibration (QEq) approach leads to charges
in excellent agreement with experimental dipole moments and with the atomic charges obtained from the electrostatic potentials
of accurate ab initio calculations. QEq can be used to predict charges for any polymer, ceramic, semiconductor,or biological
system, allowing extension of molecular dynamics studies to broad classes of new systems. The charges depend upon environment
and change during molecular dynamics calculations. We indicate how this approach can also be used to predict infrared
intensities, dielectric constants, and other charge-related properties.
1. Introduction
Knowledge of the charge distribution within molecules is essential for determining the electrostatic energies (including hydrogen bonding) in molecular mechanics and molecular dynamics
calculations.I4 Unfortunately, reliable charge distributions are
known only for a few organic molecule^.^^^ Thus, currently there
is no effective approach to estimate the charges for inorganic
systems (ceramics, zeolites, high- T, superconductors), and current
estimates of charges for polymers and large organic systems are
quite uncertain. For biological molecules, the 20 standard amino
acids and four standard bases have been assigned charges2+ that
are expected to be reasonably accurate; however, charges are not
available for nonstandard amino acids, unusual bases, and various
cofactors and substrates.
An additional serious problem is that current approachesI4 to
molecular mechanics and molecular dynamics use fixed charges
that cannot readjust to match the electrostatic environment. Since
the charges are not allowed to respond to the environment, the
tradition is to incorporate a dielectric constant in the interaction
potential, leading to additional uncertainties in the calculations.
We propose here a general scheme for predicting charges of
large molecules based only on geometry and experimental atomic
properties. The charge equilibration (QEq) approach allows the
charges to respond to changes in the environment, including those
in applied fields, and can be applied to any material (polymer,
ceramic, semiconductor, biological, metallic).
In section 11, we derive the basic equations for the charge
equilibration approach. The scaling parameter X relating atom
size to crystal atomic radii is determined in section 111 by comparing theory and experiment for the alkali-metal halide diatomic
molecules. In section IV, we discuss hydrogen atoms, which
require an extension of the simple scheme of section 11. Finally,
in section V we apply the QEq method to a number of molecules
and compare our results with experiment or ab initio theory.
The concepts involved in the QEq approach rest upon earlier
ideas of Pauling, Mulliken, Margrave, Parr, Pearson, Mortier,
and others. Section VI summarizes the relationship between QEq
and some of these earlier ideas.
In section VII, we mention some possible extensions utilizing
the ability of QEq to allow polarization of the charge distribution.
11. Charge Equilibration
* BioDcsign,
BioDesign, Inc., and Colorado State University.
Inc., and California Institute of Technology.
(Contribution No. 8340.
so that
$)Ao
= y2(1P + EA) = xi
(3)
IP - EA = J
o
u
(4)
5.343
6.899
8.741
10.874
2.843
4.168
5.463
6.928
8.564
2.421
7.790
2.331
6.822
2.183
4.5280b
F
Na
Si
P
S
CI
K
Br
Rb
I
cs
H
10.126
1 1.760
13.364
14.948
4.592
6.974
8.000
8.972
9.892
3.84
8.850
3.692
7.524
3.422
13.8904b
R. A
L au
1.557
0.759
0.715
0.669
0.706
0.4174
0.8563
0.9089
0.9745
0.9206
0.4364
0.7737
0.8257
0.8690
0.9154
0.4524
1.0253
0.5162
1.0726
0.5663
1.0698
2.085
1.176
1.102
1.047
0.994
2.586
1.141
2.770
1.333
2.984
0.371
or
XA(QI.-QN)
+'
/ ~ ~ A Q A ~
= 14.4/RoA or
RoA
(6)
UEAO
+ xOAQA)
A
XN
(8)
CQi
(=I
(9)
CD = -D
(10)
4 = -Qmt
Di = xp - xp for i 1 2
(1 1)
and
Cii =
Qi
(12)
where
JABW
-
AFBQ~Q~J~~
which we rewrite as
EQ(QI-.QN)
..e
where
(1')
= 14.4/&
= UEAO
+ XIQA+ Y*QA~JO,A)+
B F A J ~ ~ Q(7')~
N
Qtot
E(Qi-Qiv)
A Q A+
leads to an
where the x i and &A can be derived directly from atomic data.
However, the atomic IP and EA must be corrected for exchange
interactions present in atoms but absent in molecule^.^ (The
atomic states contain unpaired spins, whereas the molecules for
which we will use x A and J A generally have all spins paired.) This
leads9 to the generalized Mulliken-Pauling electronegativities and
idempotentials in Table I.
The idempotential is roughly proportional to the inverse size
of the atom, and indeed, one can define a characteristic atomic
size PAby
&A
+~
xi = x2
xOA
QA
EA(Q) = EAO
+X
(suggesting that J A A ( R )
fiAas R 0).
Taking the derivative of E with respect to
atomic-scale chemical potential of the form
Y~CQAQBJAB
(6')
A,B
@$
= N,Fle-fr
(15)
TABLE 11:
metal halide
NaCl
NaBr
NaI
KCI
KBr
KI
RbCl
RbBr
Rbl
CSCl
CsBr
CSI
LIF
LiCl
LiBr
Lil
Na F
KF
RbF
CsF
Q,Xp"
0.792
0.757
0.708
0.800
0.783
0.740
0.784
0.768
0.753
0.743
0.134
0.735
0.837
0.731
0.694
0.647
0.879
0.821
0.781
0.697
QQM~
QA-0.5
0.766
0.745
0.709
0.775
0.768
0.754
0.763
0.757
0.747
0.769
0.767
0.763
0.791
0.939
0.902
0.841
0.665
0.662
0.653
0.655
0.776
0.756
0.720
0.784
0.777
0.764
0.771
0.766
0.757
0.777
0.776
0.773
0.803
0.958
0.921
0.860
0.671
0.667
0.657
0.660
= I
2.504
2.561
2.663
2.095
2.165
2.299
1.918
1.977
2.088
1.874
1.935
2.054
6.033
c=2
0.682
0.644
0.585
0.737
0.708
0.663
0.741
0.713
0.672
0.763
0.739
0.703
0.748
0.737
0.685
0.608
0.666
0.695
0.695
0.711
13.513
13.563
14.936
1.751
1.530
1.435
1.427
=o
0.395
0.368
0.328
0.447
0.423
0.387
0.459
0.435
0.400
0.479
0.457
0.424
0.399
0.379
0.351
0.310
0.411
0.450
0.458
0.473
&,,, = 0.4913.
9.0
*a*,
14
0.420
0.391
0.350
0.473
0.448
0.411
0.484
0.460
0.424
0.505
0.482
0.449
0.427
0.406
0.377
0.333
0.434
0.473
0.481
0.496
c =
----14.4 I R
Shielded
Potentials
~ M =
X
QM
( 1 /4.80324)QuR~x
(19)
3.0
3.0
Distance
4.0
5.0
(A)
RA
(r) = (2n
+ 1)/(2{A)
(16)
= X(2n + I)/(%)
(17)
where RA is the covalent radius in atomic units (ao = 0.529 17
A) for atom A, which we select from experimental crystal structure
data (seeTable I). An adjustable parameter X is included in (17)
to account for the difference between an average atom size as given
by ( I 6) and the crystal covalent radius RA. We require that the
same X be used for all atom of the periodic table and in section
I11 determine I by comparing the predicted and experimental
dipole moments of the alkali-metal halide diatomics. The diatomic
Coulomb integral JAB involving these Slater functions is evaluated
exactly for {A and tBat the various distances.
{A
Qx = -QM
= (2n
+ 1)/(4RA)
( 17')
IV. Hydrogen
The Mulliken-like definition' * for electronegativity leads for
hydrogen to x! = '/2(IP + EA) = 7.17 eV, which is not consistent
with the Paulint2 or otherI3 empirical values for electronegativities. With xH,the hydrogen is more electronegative than C
(x$J"P= 5.34) or N (x&*P = 6.90), whereas the Pauling scale
(based on chemical experience) has h drogen much more el=tropositive than C (x; = 2.1, while xc = 2.5) and slightly more
electronegative than boron (x', = 2.0). As discussed in ref 9, the
problem with x! is that the effective EA for H is much smaller
than the atomic value because the H orbital involved in a bond
cannot expand to the value achieved in a free H- ion. Consequently, we redefine :x and JOHH for hydrogen, allowing EAH to
be a variable.
From an examination of the charges on H in the molecules LiH,
CH4, NH3, H 2 0 , and HF, we find that an accurate description
of Q H is obtained if the effective charge parameter tH is allowed
to be charge-dependent:
(20)
= ZOH + QH
Here s", = 1.0698 is based on (17) where RH = 0.371 A. The
idempotential JHH becomes charge-dependent:
{H(QH)
JHH(QH)
= (1 + QH/&)J&H
(21)
-0.05(0.04)
0240.28
4.78
0.18
029
Figure 2. (a) Predicted charges for Ala-His-Ala. The N and 0 termini are charged as appropriate for a peptide. Comparisons with charges from
AMBER^ are given in parentheses. (b) Same as (a) except that His is protonated.
exptl
0.419
0.3258
0.2678
0.150"
-0.76v
QEqb
0.462
0.353
0.243
0.149
-0.767
HFC
0.462
0.398
0.338
0.124
-0.682c
-0.44
o,1<201
00.05
QEqHFd
0.11
0.457
0.346
0.233
0.124
-0.679
'From eq 23 for xH(Q)and eq 7 for other atoms. Fitted to experimental charges; x: = 4.5280,& = 13.8904. CReference6. dFitted to
H F charges; XH = 4.7174, & = 13.4725. eCloslowski, J. Phys. Rev.
L e f f . 1989, 62, 1469. /Reference 25. #Reference 26. "Reference 27.
0.16
xi
Instead of determining the parameters in (20) with experimentally derived charges, we could use the charges calculated from
electrostatic potentials of H F wave functions. This might be more
appropriate for comparing with charges from H F calculations.
This leads to
xi
aH
= 4.7174 eV
= 13.4725 eV
(24)
and other results as in the last column of Table 111.
Equations 20 and 21 are well-behaved in the range of QH
-1.0 < QH < +1.0
(5')
corresponding to (5). (They would lead to unphysical results for
sufficiently negative values of QH.)
In solving (10) using (21), we use (20) with an estimated QH
and iterate until all QH's are self-consistent. This converges rapidly
for all cases tried (six to ten iterations for an initial guess of zero
for all cases discussed).
V. Results
To test the utility of the charge equilibration approach, calculations were carried out on a representative set of molecules
for which ab initio partial charges or experimentally derived
charges are available.s.6 The calculations were carried out at the
experimental
using the electronegativities, idem(1 4) All plyatomic geometries are from ref 15 or 16. Diatomic geometries
are from ref 10.
(15) Harmony, M. D.; et al. J. Phys. Chem. Ref. Data 1979, 8, 619.
(16) Callomon, J. H.;Hirota, E.;Kuchitsu. K.; Lafferty, W. J.; Maki, A.
G.; Pote, C. S.Londolr-B6mstein,New Series; Springer-Verlag: New York,
1978; Vol. 7.
, 0.143
-0.284
0.826
-0.828
0.823
-0.823
0.050
L?
0.1394
-0.534
0.057
Figure 4. Predicted charges for (top to bottom) polyethylene, poly(vinylidene difluoride), poly(tetrafluoroethylene), and poly(oxymethy1ene).
= f/,(IP - EA) = 7 2 4 ~
= 4*4/
(25)
Figure 5. Predicted charges for (a) Nylon 66 and (b) PEEK. For each
case, an additional unit was included on each end (to eliminate end
effects).
Ni-i3
CHI
C2H6
C2H2
C2H4
C6H6
co2
H2CO
0.46
0.35
0.24
0.15
0.16
0.13
0.15
0.10
-0.45
-0.43
0.19
0.12
0.36
-0.66
-0.15
0.14
0.18
-0.42
0.39
-0.63
0.29
0.23
-0.44
0.56
0.16
-0.65
0.38
-0.24
0.22
-0.37
0.13
-0.45
0.42
-0.23
0.13
0.08
0.19
0.32
H
H
H
H
H
H
H
0
0
C
H
H$OH
HzNC(0)H
H(0)
0
C
H,
H,
0
C
N
Hc
H,
HOC(0)H
0
C
H(C)
H(0)
HlCCN
HzC=C=O
SiH4
PH3
CIH
N
C
C
H
0
C
C
H
H
H
H
0.46
0.35
0.23
0.13
0.13
0.11
0.13
0.09
-0.45
-0.44
0.24
0.10
0.34
-0.66
-0.09
0.12
0.16
-0.43
0.42
-0.61
0.28
0.22
-0.44
0.58
0.14
-0.65
0.37
-0.25
0.22
-0.31
0.11
-0.45
0.42
-0.19
0.11
0.07
0.18
0.31
exptl
HF
0.4Ic
0.46
0.40
0.34
0.12
0.33d
0.27d
0.14e
0.171
...
0.29
0.17
-0.33
-0:45
-0.50
0.58
-0.04
0.39
-0.63
0.21
-0.01
0.04
-0.57
0.66
-0.92
0.42
0.40
-0.60
0.78
0.03
-0.67
0.46
-0.43
0.43
-0.39
0.13
-0.41
0.77
-1.08
0.36
0.06
0.15
0.25
MP2
...
0.47
...
...
0.23
...
0.22
...
...
-0.45
0.19
0.13
...
...
..,
...
...
-0.28
0.48
-0.89
0.42
0.41
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
...
PEOE
0.27
0.21
0.11
0.02
0.02
0.12
0.05
0.06
-0.19
-0.31
0.11
0.10
0.21
-0.40
0.63
0.05
0.05
-0.13
0.20
-0.37
0.16
0.16
-0.26
0.29
0.15
-0.48
0.30
-0.20
0.06
0.02
0.04
-0.23
0.12
-0.01
0.07
0.01
0.10
0.15
Del Re
0.33
0.24
0.04
0.04
0.03
0.03
0.03
-0.14
-0.14
0.05
0.04
0.30
-0.45
-0.01
0.06
0.06
-0.09
0.17
-0.52
0.22
0.22
-0.12
0.22
0.05
-0.45
0.30
-0.07
0.08
-0.12
0.04
-0.15
0.14
-0.06
0.03
0.04
0.04
...
IDME
EEM
-0.41
0.36
0.21
0.36
0.05
0.02
0.00
0.01
0.01
0.01
0.01
-0.05
-0.10
0.03
0.04
0.03
-0.58
-0.11
0.23
-0.03
0.00
0.01
0.02
0.02
-0.22
0.03
-0.05
0.04
0.04
-0.08
0.05
0.05
-0.08
0.06
-0.07
0.01
0.00
0.02
0.36
0.07
0.07
-0.10
0.02
0.02
0.03
...
...
...
= 14b
0.22
0.11
0.05
0.01
0.02
0.03
0.02
0.03
-0.1 1
-0.22
0.05
0.08
0.07
-0.26
0.01
0.06
0.06
-0.24
0.06
-0.10
0.09
0.09
-0.18
0.12
0.12
-0.19
0.13
-0.14
0.00
-0.01
0.05
-0.23
0.05
0.03
0.07
0.02
0.08
0.16
= Ib
-1.00
-1.00
-0.11
-0.02
-0.05
...
-0.08
0.04
-0.15
-0.34
-0.11
0.22
-0.51
0.22
0.24
0.06
-0.06
-0.33
-0.20
0.30
0.04
-0.21
...
...
...
...
...
0.15
-0.36
0.06
0.05
...
...
...
...
-0.07
-1.00
-1.00
= 2b
0.36
0.23
0.13
0.05
0.04
0.06
0.05
0.05
-0.29
-0.3 1
0.14
0.09
0.20
-0.42
0.00
0.07
0.08
0.27
-0.35
0.19
0.17
-0.31
0.35
0.10
-0.40
0.25
-0.21
0.13
-0.16
0.08
-0.34
0.26
-0.13
0.11
0.06
0.15
0.26
'Carpenter, J. E.;McGrath, M. P.; Hehre, W. H. J . Am. Chem. SOC.1989, I l l , 6154. *From eq 25. cReference 25. dReference 26. !Reference
27. Buckingham, A. D.; Disch, R. L.; Dunmur, D. A. J . Am. Chem. SOC.1968, 90, 3104.
assumes that electrostatic interactions can be built upon a molecular connectivity framework. Thus the extension to salts is not
apparent. Partial charges reported by Allinger and co-workers
are provided in Table 1V in the column labeled IDME. The
charges calculated by this approach appear to underestimate
charge transfer from hydrogen by a factor of 2 (e.g., 0.07 on H
in CH, and CzH6compared with 0.15 and 0.17 for experimentally
derived charges).
VII. Properties
In addition to calculating electrostatic energies and multipole
moments, the self-consistent charges can be used to evaluate the
other properties such as infrared or Raman intensities. For example, if we express the a component of the dipole moment as
~u
= E Qi&
(26)
ZAikQk = -Bi
k
we can write
where (for i # 1 )
aJlk
aRj,
VIII. Summary
The charge distributions from charge equilibration (QEq) lead
to good agreement with experiment. The QEq approach uses only
readily available experimental data (atomic IP and EA, atomic
radius) and thus can be applied to any combination of atoms. (The
relevant x and J values have been tabulated for all elements
through L W . ~ ~The
~ ~ results
)
for simple examples of typical
organic, inorganic, biological, and polymer systems seem reasonable, and we believe that this approach will prove valuable in
simulating biological, polymer, and inorganic materials.
Acknowledgment. These studies were initiated while A.K.R.
was on sabbatical at BioDesign, and we thank the BioDesign staff
for useful discussions. We also thank BioDesign for the use of
BIOGRAF in carrying out these calculations. Partial funding for
this research (W.A.G.) was provided by a grant from the Air Force
Office of Scientific Research (No. AFOSR-88-005 1).
Using (IO)
aAik
aJik
-.=--aRj, aRj6
(29)