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structure of (N2)2
Rut M. Berns and Ad van der Avoird
Citation: The Journal of Chemical Physics 72, 6107 (1980); doi: 10.1063/1.439067
View online: http://dx.doi.org/10.1063/1.439067
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/72/11?ver=pdfcov
Published by the AIP Publishing
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The short range electrostatic and (first order) exchange contributions to the N2-N2 interaction energy
have been calculated ab initio as a function of the N2 orientations and the distance (139 geometries).
Using a numerical integration procedure, the results have been represented analytically in the form of a
spherical expansion. At R = 0.3 nm this expansion is accurate to better than 0.5% if we include the first
18 independent terms, to 2% if we truncate after LA = LB = 4, and to 16% if we truncate after
LA = LB = 2. In combination with the long range multipole expansion results (electrostatic R -s, R -7,
R -9 terms, dispersion R -6, R -8, R -10 terms) calculated by Mulder et aI., this yields an anisotropic
N2-N2 interaction potential in the region of the van der Waals minimum, which can be fairly well
represented also by a site-site model. The potential is in good agreement with the available experimental
data for the gas phase and for the ordered (a and r) crystal phases of solid N 2 . The structure of the van
der Waals molecule (N2)2 is discussed; its energy is lowest for the crossed structure: ..:iEm = 1.5 kllmol,
Rm = 0.35 nm (for the isotropic potential the well characteristics are ..:iEm = 0.75 kl /mol and Rm = 0.417
nm). The (staggered) parallel and the T -shaped structures are slightly higher in energy. The interual N2
rotation barriers vary from 0.2 kllmol (17 cm- I ) to values comparable with the dissociation energy.
I. INTRODUCTION
(1 )
6108
monomer Hamiltonians, respectively; <l is the normalized antisymmetrizer of the dimer. For the expansion of the MO's the atomic orbital (AO) basis set D of
Mulder et al. ,3 including two d -type polarization functions' has been used. This large basis is necessary
in order to obtain reliable molecular multi pole moments. 3
This first order energy 6.E(1) can be separated into an
electrostatic component, 6.E~~!c, defined by (1) with the
operator <l replaced by tIE identity, andanexchangecomponent defined as
6.E~!~h = 6.E( I)
6.E~~~c .
For large intermolecular distances, one can approximate 6.E~~!c by a power series in R by substituting the
multi pole expansion for the interaction operator VAB
=SAB _SA _SB:
.. , =L'"
+L
~O
a=O
boO
b~O
For large intermolecular distances one can again substitute the multi pole expansion for VAB and obtain the
series:
"
with n = 6, 8, 10, etc. The charge penetration effect is
defined by the difference
6.E~~! = 6.E(2) - 6.E~Jlt .
AEIl)b
AEU) b
ncb
AE(1) b
AE(j)
(kJmol- t )
(kJmol- t )
.lee
""It
(kJmol- t )
(kJmol- t )
90',90',0'
0.331
0.357
0.384
0.410
0.437
3.991
1. 562
0.640
0.291
0.154
4.481
1. 564
0.531
0.176
0.056
- O. 490
- O. 002
0.109
0.115
0.098
0.375
0.259
0.187
0.139
0.105
3.519
1. 331
0.505
0.201
0.089
4.154
1. 461
0.499
0.166
0.054
- O. 635
- 0.130
0.006
0.035
0.035
0.134
0.096
0.071
0.053
0.040
45',45', 0'
0.331
0.357
0.384
0.410
0.437
15.619
5.753
1. 975
0.588
0.109
21. 689
7.985
2.855
0.992
0.335
27.187
10.440
4.045
1. 625
0.706
35.132
12.508
4.340
1. 469
0.484
-7.945
- 2.068
- O. 295
0.156
0.222
104.589
43.925
15.959
6.299
2.586
1. 152
0.582
0.340
0.224
142.630
55.629
18. 882
6.600
2.249
- 38.041
- 11. 704
- 2. 923
- O. 301
0.337
17. 515
6.345
2.133
0.613
0.099
24.113
8.718
3.067
1. 050
0.349
6.070
2. 232
0.880
O. 404
O. 226
6. 598
2. 373
O. 934
O. 437
O. 250
O. 649
O. 467
O. 337
O. 246
O. 182
1. 391
0.889
0.593
0.409
0.291
4.177
2.525
1. 601
1. 057
0.721
O. 747
0.533
O. 384
O. 280
O. 208
6109
f_ __L.~
0A' BB'
R(nm)
-1.0
<PA
~,~At,indc
M(2) b
dUp
ae!,i/lt,dt8P c
(kJmo[-I)
(kJmo[-I)
(kJmo[-I)
(kJmo[-I)
90. 90. 0
0.331
0.357
0.384
0.410
0.437
- O. 070
-0.018
- O. 007
- O. 003
- 0.002
- O. 015
-0.009
- O. 005
-0.003
- O. 002
- 5. 045
-3.074
-1. 931
-1. 250
- O. 833
- 5. 046
- 3. 009
-1. 877
- 1. 216
- O. 813
90. 900. 90
0.331
- 0.066
- O. 019
-4. G06
-4.654
45. 45. 0
0.331
-1. 462
- O. 042
- 10. 162
- 10. 099
45. 135. 0
0.331
-2.858
- O. 076
-12.528
-11.417
-17.996
- O. 312
- 24. 899
-19.314
-1. 250
-0.097
- 10. 033
- 9. 629
0, 0, 0"
0.331
-2.0
M(2)b
\pd
0. 90. 0
0.331
-3.0
-4.0
-s.o
FIG. 1. Different contributions (as defined in the text) to the
interaction energy between two parallel N2 molecules; ab initio
results, see Tables I and II.
minimum. (This minimum lies at R = O. 417 nm for the
isotropic potential, see below, and . at R = 0.36 nm for
the parallel dimer, see Fig. 1). This conclusion agrees
with the penetration effect calculations by Ng et al. 10
The second order interaction energy has been calculated for ten geometries only, see Table II and Fig. 1.
We have found, just as Mulder et al. ,3 that the induction
energy can be neglected with respect to the dispersion
energy. The second order penetration energy is much
smaller than the corresponding first order contribution.
Therefore, the second order energy can be well represented by the dispersion multi pole series, 6.E~Jlt,dlW
Mulder et al. 3 have pointed out, however, that the dispersion multipole coefficients obtained by the uncoupled
Hartree-Fock perturbation method (but also by other
perturbation methods starting from Hartree-Fock mono-
LA~LB
(LA,LB,L
V LA ,LB,L(R)(2-6 LA,LB)
8UD)
Xt[ALA.LB,L(WA, WB,
U) +ALB.LA.L(WA, W B , U)]
(3a)
6110
!H{kJ/moll----------------------.:.------.\
0.0
t---.....,----.....,...... .,Io:---....,.--......~"=""----....,.-~
0.35
0.50
\
\
0.55 R(nm)
I-;;-~~~--=----
"~---
-0.5
-e-
-1.0
ab initio
spherical
expansion
-'.5
LA
LB
L)
MA
MB
(4)
L: L: Vii
lEA
J EB
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6111
m.
IT
Parameters
Electrostatic:
0.373e b
0.0847, 0.1044
0.37ge b
O. 0848, 0.1041
Short range
repulsion:
(exchange
+ penetration)
A (kJmol-1)
770000
40.37
0.0547
559000
39.49
0.0547
Dispersion:
8 (om-I)
force centers C zSR(nm)
O. 001511(0. 001407)d
0.0471
aMolecular multipole moments calculated with this point charge model: Q2,O = - 4.449 10-40 C m 2 Q4,0
=-8.046 1O-s0 C m4, Qs,o=-11.0631O-80 C mS. ao initio (Ref. 3): Q2,O=-4.487 10-40 C m 2, Q4,O
=-9.23310-60C m4, Qs,o=-6.1291O-80 C mG.
be = 1. 602 10-19 C.
COptimized force centers zSR=O. 0554 nm practically coincide with the nuclear positions zN = O. 0547 nm.
<lrn parentheses: optimized parameter C if the force centers are fixed on the nuclei, zD=O. 0547 nm.
(0 The charges q=q+= -q. and the position parameters z+ and z_ have been found by fitting LILJqlqJrj} to
~E~~lt, calculated up to K9 terms inclusive, using the
multipole moments of Ref. 3 (mean deviation 6. 5% for
36 points).
(ii) The parameter C = C N -
and the positional parameter of the r- s force centers have been found by fitting
LILj Cr i~ to ~E};Jlt, calculated up to R- IO terms inclusive
from the multipole coefficients of Ref. 3, Table VI,
(mean deviation 6.3%. or 9.7% if the force centers were
fixed on the nuclei).
llE (k l/mol)
I
3.0
IR=0. 4nm
l!I
2.5
2.0
1.5
1.0
0.5
0.0
-0.5
(I) I
f1 E mult.(electrostatic I
I
I
-1.0
expansion
-1.5
-2.0
fiE
(2)
mult.(dispersionl
i
-2.5
,,
30
60
<P;:::;t"8
60_30
08
60
30
8A
6112
II dbA(l -1
b~y1/2
arccosTiB, arccosbA;R) .
Rmtn
-1.0
(nml
0.55
,
/
0.50
/
/
-1.5
'ab initio'
0.45
0.40
0.35
-2.0
.J<"1G. 4. Orientational dependence of the van der Waals minimum. The well depth ~mln and equilibrium distance Rmm
have been obtained by varying R for each orientation 6 A' 6 B,
<i>A. "Ab initio," spherical expansion, and atom-atom potentials defined as in Figs. 2 and 3.
This integral is very suitable for numerical integration. The best method for our purpose (which is to apply it to ab initio results) is one of the Gaussian integration techniques, since these give the highest accuracy
with the smallest number of integration points. 19 For
Legendre (unctions it is best to choose the GaussLegendre modification. (Parker et al. 20 have used this
technique in a one -dimensional integration required to
obtain the Ar-CO potential.) We have used formulas
(25.4.30) and (25.4.38) of Ref. 21. Since we only have
to find the spherical expansion of the short range contributions t:..E~~~ and t:..E~!~h (see Sec. mAl, we have applied this integration method to the exponential part of
the site -site potential, Sec. III B, term (iii). Some
experimentation with the grid and with the expansion
length has led to the (ollowing conclusions. (1) The
first 18 terms in the spherical expansion are necessary
to represent the short range potential to an accuracy
better than one percent in each point. (2) The required
number of integration pOints for (TiA, 17B, bA) is (6,6,5).
TABLE IV. Spherical expansion coefficients Eq. (4)
of the short range (penetration and exchange) interaction energy.
ab initio a
atom-atom b
0, 0, 0
44.258
49.769
2, 0, 2
23.871
26.936
2, 2, 0
2, 2, 2
2, 2, 4
2.947
-4.734
13.154
3.674
- 5. 794
14.667
4, 0, 4
4.309
3.551
4, 2, 2
4, 2, 4
4, 2, 6
0.314
0.380
- O. 732
- O. 701
3.151
2.520
4,
4,
4,
4,
4,
0
2
4
6
8
0.005
- O. 006
0.026
- 0.131
1. 035
0.033
- 0.107
0.573
6, 0, 6
0.389
0.264
6, 2, 4
6, 2, 6
6, 2, 8
0.011
- O. 057
0.399
- O. 049
4,
4,
4,
4,
4,
0.010
- O. 015
MA=O
XP~~(COSfiA)P1~(COSfiB)COSMAcf>A ,
where the P~ are associated Legendre functions. 14 (2)
Using the symmetry properties of the system reduces
the integration intervals. Since the angular functions
0.018
0.250
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6113
2, 0, 2
1. 849 10-3
2, 2, 0
4, 2, 6
Dispersion
cfA,LB,L
(kJ mol- t nm 6)
CLA,LB,L
to
23110-3
-2.946 10"
-2.23910-5
-5.27710"
-5.97410-6
-3.63810-5
-4.50510-6
-3.76410-6
-4.93210-6
1. 026 10-6
-6.09810-1
- 4.
0, 0, 0
2, 2, 4
2, 2, 2
C;A,LB,L
7.655 10-5
4, 4, 8
6.078 10-6
6, 2, 8
8.46510-1
aNote that the long range multipole coefficients C;A,LB'L defined in this paper are different from
the C;A,LB,JI of Ref. 3; the two definitions are, of course, related by a simple linear transformation.
with the long range results, 3 yield a fairly good representation of the ab initio calculations for the N2 -N2 interaction potential (see Figs. 2 and 4).
IV. APPLICATIONS OF THE N 2-N 2 INTERACTION
POTENTIAL; COMPARISON WITH EXPERIMENTAL
DATA
A. Isotropic potential
Our calculated isotropic N2 -N 2 potential, Vo,o,o(R),
can be compared with some empirical isotropic potentials from gas phase virial coeffiCients, viscosity data,
and from solid state properties. 22 Since the latter have
only been determined in the Simplified forms of Lennard-Jones (12-6) or Buckingham (exp - 6) potentials,
we shall not compare the shape of the potentials but
only their main characteristics: the scattering diameter (a), the equilibrium distance (Rill), and the well
depth (~EIII)' The results listed in Table VI show that
the agreement is good, so that we expect our calculated
potential to explain quantitatively the experimental bulk
data (at least those which have been used to determine
the empirical poten tial parameters).
B. N2 crystal properties
Our site-site potential fitted to the ab initio data (Sec.
III B) has been used to calculate the equilibrium structure and the cohesion energy of the ordered (a and y)
phases of solid N2 The results, unit cell dimension
a = O. 561 nm for the cubic a phase, cohesion energy 6.43
kJ/mol (corrected for the zero-point lattice vibrations),
and a = O. 403 nm, c = O. 500 nm for the tetragonal y
phase, are in good agreement with the experimental
data, 1,2 a = O. 564 nm, heat of sublimation (at 0 OK) 6. 92
kJ/mol for a-N2' a=O. 396 nm, c=O. 510 nm for y-N 2
Also the phonon frequencies at various wave vectors, obtained from harmonic or self -consistent phonon lattice
6114
(run)
Rm(nm)
Calculated Vo,o,o(R)
(Table V)
0.376
0.417
0.748
Lennard-Jones (12-6)
from virial coefficients
(Ref. 22, p. 209)
0.370
0.415
0.793
Lennard-Jones (12-6)
from viscosity data
(Ref. 22, p. 209)
0.368
0.413
0.763
Buckingham (exp - 6)
from virial coefficients
and crystal data
(Ref. 22, p. 181)
0.363
0.404
0.947
Buckingham (exp - 6)
from viscosity data
(Ref. 22, p. 181)
0.362
0.401
0.844
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15:05:39
6115
R (nm)
8A
<PA
AE (kJmorl)
90
90
90
1. 35 a (1.46, b 1. 52")
neighbor pair
0.399 (0.404")
90'
35
55'
1. 05 (1. 05")
crystal d
neighbor pair
0.379 (0.398")
90
42
90
Most stable
dimer structure a
d
Ci -N2 crystal
"y-N2
aNeglecting the energy of the nuclear motions; complete search of the potential energy surface has
been performed with the atom-atom potential I of Table III.
byrom the spherical expansion, Table V.
cFrom the aIJ initio first order energy (Table n and the second order energy from the dispersion
multipole coefficients of Ref. 3 (Table Vn, s'ee Table V and Fig. 2.
dExperimental crystal structure, see Ref. I, nearest neighbor pair energy ~ calculated with
atom-atom potential I.
R mln and AE miD obtained with the atom -atom potential I (Table III) for fixed N2 orientations from
Ref. d.
= 0.42
Note added in proof. After completion of this manuscript we have received a pre print by Ree and Winter, 29
also containing ab initio results for the N 2 -N2 potential.
These authors have concentrated on the short range,
strongly repulsive, region of the potential. The smaller
basis set which they have used (overestimating, for instance, the N2 quadrupole moment), in combination with
the supermolecule self-consistent field (SCF) method
(leading to some basis set superposition error), is less
adequate for the long range and for the region of the van
der Waals minimum, on which we have concentrated.
Moreover, they have not included the dispersion energy
contribution.
ACKNOWLEDGMENTS
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6116
1964).
21'. Luty, A. van der Avoird, and R. M. Berns (to be published) .
24C. A. Long, G. Henderson, andG. E. Ewing, Chern. Phys.
2, 485 (1973).
25A. KoideandT. Kihara, Chern. Phys. 5,34(1974).
26K. Sakai, A. Koide, and T. Kihara, Chern. Phys. Lett. 47,
416 (1977).
27S. E. Novick, P. B. Davies, T. R. Dyke, and W. Klemperer,
J. Am. Chern. Soc. 95, 8547 (1973).
28J. M. Steed, T. A. Dixon; and W. Klemperer, J. Chern.
Phys. 70, 4940 (1979).
29 F . H. Ree and N. W. Winter, J. Chern. Phys. (submitted
for publication).