Chemical Physics 155 ( 199 I ) 35 1-356

North-Holland

Structure and dynamics of polar liquids:

a molecular dynamics investigation of N,N-dimethyl formamide
S. Yashonath and C.N.R. Rao
SolidState and Structural Chemistry Unit, Indian Institute ofscience, Bangalore 560 012. India

Received 26 November 1990; in final form 25 March 199 I

A molecular dynamics study of liquid N,N-dimethyl formamide has been carried out. Orientational correlation functions sug-
gest a stacked antiparallel ordering at short distances ( < 5 A) and a perpendicular + configuration at intermediate distances. The
proposed ordering is in agreement with the recent ‘-‘CNMR results of Konrat and Sterk and suggests a stronger association of
CH,(t ) with 0 than of CH,(c) with 0. Both the translational and the rotational motions are anisotropic. The diffusion constants
for rotation along the different directions are different, in agreement with the NMR results.

1. Introlluction We considered it most worthwhile to carry out a

The importance of dipolar interactions in deter-
mining the structural and dynamical properties of
polar liquids such as DMF has not been examined in
detail hitherto, although a theoretical framework has
been suggested for these interactions recently [ 11.
There have been several experimental investigations
of the anisotropic molecular motion in the liquid state
by employing 13C NMR and quadrupolar relaxation
[ 2-41, and such studies have been carried out on liq-
uid N,N-dimethyl formamide (DMF) as well [ 5-71.
Liquid N,N-dimethyl formamide, in contrast to
formamide and dimethyl acetamide, cannot undergo
self-association due to hydrogen bonding and there-
fore provides a good system to investigate dipolar in-
teractions in the liquid state. The study of Nakanishi
and Yamamoto [ 5 ] on DMF has shown that there is
a significant difference between the rotational fre-
quencies of the trans-methyl, CH3( t ), and the cis-
methyl, CH, (c). Quadrupolar relaxation studies of
Wallach and Huntress [ 71 show that considerable
anisotropy exists in the rotation frequencies of the
molecule as a whole relative to the free molecule.
These results have received further confirmation in
the recent NMR study of Konrat and Sterk [ 6 1. Jor-
gensen and Swenson [8] have calculated the ther-
modynamic properties of amides by employing the
Monte Carlo method.
molecular dynamics simulation on liquid DMF to
understand its liquid structure and dynamics. An im-
portant aspect of interest to us was to obtain infor-
mation on the near-neighbour structure by means of
site-site radial and orientational correlation func-
tions. It was of equal interest to simulate the aniso-
tropic translational motion and the reorientational
motion and understand the role played by dipolar in-
teractions in determining the anisotropy of reorien-
tational motion. Earlier computer simulations of
DMF have been limited to the calculation of the ther-
modynamic properties by employing the Monte Carlo
method [ 8 1.
2. Computational details and intermolecular potential
functions
All the calculations were carried out in the micro-
canonical (N, V, E) ensemble. The integration was
performed by a fifth-order predictor-corrector algo-
rithm. The orientations were represented by quater-
nions. Periodic boundary conditions were imposed
and Ewald sums employed to calculate the slowly
converging Coulomb interactions. Equilibrium was
reached after 10 ps and properties calculated over 20
ps. The calculations were carried out on 64 mono-
mers with a cut-off radius of 9 A. Even though the

0301-0104/91/$03.50 0 1991 Elsevier Science Publishers B.V. All rights reserved.

352 S. Yashonarh, CXR. Rao iStructure and dynamrcs ofpotar @ids

number of monomer employed in the calculations is

small, it is to be noted that it is large enough to per-
mit a cut-off radius that is comparable to the usual
2.5~ employed in monatomic simulations. The time
step of the integration was I fs and the temperature
in the simulation was 294 K.
Several intermolecular potential functions are
available in the literature for amides [ 8- 13 1. These
potentials have been well tested and known to repro-
duce the properties of amides reasonably well. Hence,
in the present work we have opted for one of the
known potentials. Most of these potential functions,
however, concern the local conformation and not in-
termolecular interactions. The EPEN/2 [ 91, Jorgen- Cf-$(t)
sen-Swenson [ 8 ] and Hagler-Lifson [ 11,12 ] poten- Fig. I. The direction of the reference frame and the details of
tials yield inte~olecular interaction potentials for molecular geometry of DMF are shown. The dipole moment is
along the x-axis (~=4.45 D). Bond lengths are in A and angles
amides, useful in statistical-mechanical computer
in degrees.
simulation studies such as the present one. The
EPEN/2 intermolecutar potential function [ 91,
however, does not reproduce the energies of crystals sen-Swenson potential [ 8 ] is 4.45 D. The geometry
of amides satisfactorily. The potential functions of and the reference frame employed by us are depicted
Clementi and co-workers [ 131 are derived from ab in fig. 1.
initio calculations; although they are usually satisfac-
tory in reproducing properties of dimers and smali 3. Results and discussion
clusters, they are unlikely to be successful in predict-
ing the properties of the liquid. Between the Jorgen- 3.1. Structure
sen-Swenson [ 8 ‘Jand Hagler-Lifson [ 11,12 ] poten-
tials, we chose the former since it is simpler and The thermodynamic results obtained in the pres-
computationally economical. It also reproduces the ent study are listed in table 2. The heat of vaporiza-
density, energy and other thermodynamic properties tion obtained by us (46.5 kJ mol-’ ) is comparable
of the liquid reasonably well. In the Jorgensen-Swen- to the experimental value of 43.5 kJ mol-’ at a some-
son potential an interaction site is usually assigned to what higher temperature of 373 K and the same den-
the positions of ail the nuclei except hydrogen. For sity [ 14 J. The therm~ynamic results obtained by us
the methyl group, there is only one interaction site, generally compare well with those from the isother-
located at the position of the methyl carbon. The de- mal isobaric Monte Carlo calculations of Jorgensen
tails of interaction parameters employed are listed in and Swenson [ 8 1. The molecular dynamics simula-
table I _The dipole moment resulting from the charges tion runs were not long enough to obtain reliable es-
assigned to various groups with the use of the Jorgen- timates of the heat capacity. Radial distribution
functions (rdfs) between the different groups were
Table I calculated and were found to be similar to those ob-
Potential parameters for N,N-dimethyl formamide a) tained by Jorgensen and Swenson [ 81. In fig. 2 we

Group fJ (A) t (kJ/mol) 4

Table 2
CO 3.75 0.4394 0.5 Thermodynamic results for N,N-dimethyl formamide
0 2.96 0.8788 -0.5
N 3.25 0.7115 -0.57 T(K) U &J/mol-‘) AL (kJ/mol-‘)
C%(t), CH,(c) 3.80 0.7 I 15 0.285
294.2 -44.1 46.5
a) From ref. [S].
 S. Yashonath.C.N.R. Rao /Structure and dynamicsofpoiar liquids 353

noticed, even though they might have some effect on

the structure of the liquid state.
Of the CH,(t)-0 and CH,(c)-0 rdfs, the former
is more intense than the latter. Konrat and Sterk [ 6 ]
have recently found that the CH3( t ) methyl group
0.
rotates about ten times slower than the CH,(c)
methyl group and have suggested this to be due to the
preferential association of CH, (t ) with the 0 of the
neighbouring molecule. Our present results are con-
sistent with this suggestion. The analysis of orienta-
0.
tional correlation functions presented below throws
light on the nature of the nearest and next-nearest

0 !L neighbour arrangements.
Orientational ordering of molecules can be dis-
cussed in terms of the orientational correlation func-
tion @zzoz(r), @zzo(r) definedas [ 171,
r 0. 5
ol

%X(r) = -$ (3(1,-i)2+3(~2-i)2-2) ,

0I

0.5 @220(r) = &j (3(~,-tz)*-l) >

where the angular brackets denote an ensemble av-

01 erage value per pair for molecular pairs with centre-
of-mass separations in the range r to r+dr, i is a unit
0.5
vector along the line joining the centre of mass and
t, and Z2 are unit vectors perpendicular to the molec-
7 I I I I I ular plane of molecule 1 and 2. The two orientational
O2 6 10 correlation functions, Qzo2(r) and 0220(r), are shown
r.A
in fig. 3; these functions take on values of 0.40 and
Fig. 2. Rdfs for liquid DMF: (a) N-N, (b) C-N, (c) O-O, (d)
0.43, respectively, near 3.5 A. Both the correlation
CH,(c)-Oand (e) CH,(t)-0.
functions are positive, implying that the orienta-
tional ordering up to about 5.5 8, is that in which the
show some of these rdfs that are relevant to the sub- molecular planes of the neighbours are nearly paral-
sequent discussion. The N-N and C-N rdfs show lel and stacked over one another [ 17 1. Based on the
characteristics of sites which are not easily accessible rdfs and the orientational correlation functions, we
to neighbours; these rdfs show a single broad peak at propose the arrangement shown in fig. 4a for the
a relatively large distance of 5-6 A. This behaviour is nearest neighbours which may be described as a
very similar to that observed in our earlier study on stacked antiparallel arrangement. The preferential
isopentane [ 15,161. The other groups such as the association of CH, (t ) with the 0 of the neighbouring
CH,(t)-0 and O-O show characteristics typical of molecule compared to CH,(c), as indicated by the
peripheral groups. The important characteristics of rdfs (fig. 2 ) as well as the NMR results [ 6 1, also sup-
the rdfs involving such peripheral groups include the ports this arrangement. Beyond about 5.5 A. both azo2
appearance of peaks at a relatively shorter distance and @2220 are negative. This situation arises when both
than found for rdfs involving the more inaccessible the molecular planes are perpendicular to each other
groups and the presence of a shoulder next to an in- and to the line joining their centres of mass. This is
tense peak. It is known that DMF can form weak valid for the + shaped arrangement shown in fig. 4b.
C-H...0 hydrogen bonds. These are too weak to be The orientational ordering shown in fig. 4a has a fa-
354 S. Yashonath, C.N.R. Rao / Srructure and dynamics ofpolar liquids

distances in the 3.5-4.2 A range corresponding to the

(a)
distance at which the potential is minimum. How-
ever, we should note that such an orientational or-
dering need not be always stable. An example of this
IT
z is the orientational ordering of nearest neighbours in
* 02- liquid benzene where the quadrupolar interactions
destabilize this ordering and instead favour a T-
shaped arrangement. Fig. 5 shows a display of an in-
I I stantaneous configuration of the liquid, looking down
8 10
(b) the z-axis.

3.2. Dynamics

In fig. 6 we show the velocity autocorrelation func-

tions for the centre-of-mass velocity components
along the x-, y- and z-directions. The motion along
the dipolar axis direction takes place without too
many collisions (see lig. 6a). In the direction perpen-
dicular to the dipolar axis and lying in the plane of
the molecule we find that the molecule encounters
more collisions. Fig. 6c suggests that the molecule en-
counters the maximum number of collisions along the
r.A direction perpendicular to the dipolar axis and to the
Fig. 3. Orientational correlation functions for liquid DMF: (a)
molecular plane. Unfortunately, no experimental in-
%2(r), (b), @&r).

(01 (bl

Fig. 4. The most probable orientational ordering in liquid DMF

suggested on the basis of orientational correlation functions: (a)
for nearest neighbours below 5 A, (b) for neighbours between
5.5 and 6.5 A.

vourable dipolar interaction. This ordering is also fa-

voured geometrically since this gives the closest
packing of neighbours. This ordering, again, is likely
to be the most favourable ordering for short-range in- Fig. 5. A display of an instantaneous configuration observed in
teractions, because of the large number of site-site liquid DMF at 294 K.
 S. Yashonath, C.N.R.
Rao /Structure and dynamics ofpolar liquids 355

(0)
0.8

0.6

\___ _ -- H
I I I I
2 4 6 8
(b)
0.8

0.6

0.4

0.2

aI- \ -‘--u
I I I
r 2 4 6 8 (cl
at t’-
0.ti --

0.d:
,-
5.i

I
2 4 6 8
I*ps
Fig. 6. Centre-of-mass velocity autocorrelation functions: (a) for
velocity component along x-axis, (b) for velocity component
along y-axis and (c) for velocity component along z-axis.
vestigation of the translational diffusive motion is
available in the literature.
The angular velocity autocorrelation function is
shown in fig. 7a. The angular velocity autocorrela-
tion function for the component of angular velocity
along the x-, y-, and z-axis are respectively depicted
in fig. 7b, 7c and 7d. The diffusion equation would
be valid for motion in the liquid in the limit that the
molecular reorientation is much slower than in the
free gas. If an exponential decay is assumed, the char-
acteristic decay time for the correlation function
works out to be ri= (60) -I, where D is the diffusion
constant. Konrat and Sterk [6] found that the reo-
rientation of DMF around the z-axis is most hind-
ered while that around the x-axis is least hindered;
t,ps
Fig. 7. Angular velocity autocorrelation functions (a) for total
angular velocity, (b) for angular velocity around the x-axis, (c)
for angular velocity around the y-axis and (d) for angular veloc-
ity around the z-axis.
reorientation around the y-axis is hindered only to a
limited extent. The angular velocity autocorrelation
functions depicted in fig. 7 suggest that the x-com-
ponent of the angular velocity is relatively free from
collisions in comparison with the y- and z-compo-
nent of the angular velocity. Thus, the velocity auto-
correlation functions for the angular velocity com-
ponents along the y- and z-axis display a small dip
around 0.6 ps, which is absent in the x-component.
We, however, point out that the experimental dipole
moment is slightly smaller than obtained by us here.
Hence, the correlations might be slightly magnified.
The trend observed by us, however, is in good agree-
ment with the NMR results of Konrat and Sterk [ 61.
In conclusion, the nearest-neighbour orientational
ordering in liquid DMF involves a stacked parallel-
plate arrangement with dipoles aligned in opposite
356 S. Yashonath, C. N. R. Rao /Structure and dynamics of polar liquids

directions. This is the preferred orientational order- [ 61 R. Konrat and H. Sterk, J. Phys. Chem. 94 ( 1990) 129 1.
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1219.
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