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Theory of bonding in transition-metal carbides and nitrides

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PHYSICAL REVIEW B VOLUME 48, NUMBER 16 15 OCTOBER 1993-II

Theory of bonding in transition-metal carbides and nitrides

J. Haglund
Department of Theoretical Physics, Royal Institute of Technology, S-IOO gg Stockholm, Sweden

A. Fernandez Guillermet
Consejo Nacional de Investigaciones Cientificas y Tecnicas, Centro Atomico Bariloche,
8/00 San Carlos de Bariloche, Argentina

G. Grimvall and M. Korling

Department of Theoretical Physics, Royal Institute of Technology, S IOO-gg Stockholm, Sweden
(Received 15 January 1993; revised manuscript received 12 May 1993)
This paper deals with the bonding properties of 3d-, 4d-, and 5d-transition-metal carbides and
nitrides. We consider NaCI-structure compounds, MC and MN, as well as carbides and nitrides with
more complex crystal structures. The enthalpies of formation at zero temperature A H(0) of the
MC and AN compounds are taken from previous ab initio linear-mufBn-tin-orbitals calculations. We
describe the structure as formed by a metal fcc lattice in which nonmetal atoms have been inserted
at interstitial positions. 4 H(0) is divided into contributions from (i) formation of the metallic fcc
lattice, (ii) expansion of this lattice to the lattice spacing of the compound, and (iii) insertion of
nonmetal atoms into the metal lattice. E H(0), plotted versus the position of M in the d series,
shows a pronounced maximum for the Ti, Zr, and Hf carbides. In agreement with other work, we
interpret this as due to the filling of bonding p dhybri-dized states. The maximum in A H(0) is
followed 6rst by a decrease and then by an almost constant value. We interpret this as an efFect of a
gradual population of antibonding and nonbonding electronic states. Size e8'ects, i.e. , contribution
(ii), are small for the 4d- and 5d-series compounds. E H(0) of MN is similar to that of MC, but
the largest values occur for M=Sc, Y, La since N has one more valence electron than C. Bonding in
the complex carbides and nitrides is given an analogous interpretation.

I. INTRODUCTION tio calculation has also been performed for Fe3C. In the
present paper, we rely on these results in an analysis
The fundamental problem of understanding cohesion of cohesive properties and bonding energies. Although
and bonding in solids can be approached in many ways, our previous works contain values both &om theoreti-
leading to different kinds of insight. The bonding cal calculations and from assessments of thermodynamic
strength is often measured by a single quantity, e.g. , the information, the discussion in this paper will be based
enthalpy of formation 4 H or the cohesive energy E, h. only on cohesive properties as obtained from ab initio
It may be instructive to divide 4 H or E, h into sep- linear-muffin-tin-orbitals (LMTO) band-structure calcu-
arate contributions that can be given simple interpreta- lations. This is sufhcient for our purposes since we have
tions. The separation is not unique, and its relevance shown that ab initio calculations, when correctly inter-
should be tested on a large number of materials. Ab preted, yield cohesive energies and enthalpies of forma-
initio electronic-structure calculations provide a useful tion in good agreement with experiment, except for an
and flexible tool for such studies, but at present they almost constant energy shift.
yield results that contain significant errors. A theoret- The NaCl structure compounds formed by metals
ical discussion of bonding mechanisms should therefore with C and N are often referred to as interstitial
be preceded by a detailed comparison between ab initio compounds. They are then conceived as a metallic lat-
results and experimental information in order to get a tice in which nonmetal atoms have been inserted at inter-
good understanding of the discrepancies between theory stitial positions. In order to accommodate the nonmetal
and experiment. atoms, the metallic lattice may have to expand, thus re-
We have recently carried out extensive ab ini- ducing part of the energy associated with metal-metal
tio electronic-structure calculations and assessments bonds. Here, we adopt this view in a quantitative study
of thermodynamic information on 3d-, 4d-, and Gd- of contributions to the bonding energy. We distinguish
transition-metal carbides and nitrides in the NaC1 crystal between (i) the energy corresponding to the formation of
structure, altogether 48 compounds. Further, we have a metal fcc lattice from free metal atoms, (ii) the energy
considered thermodynamic information on the cohesive change when expanding this lattice to the lattice spacing
properties of complex 3d-transition-metal (M) carbides of the carbide or nitride, and (iii) the change in chemi-
M&C2 ) M2C M7C3 M5C2 MBC and M23C6 and on
&
cal bonding energy due to insertion of nonmetal atoms
some complex 3d-transition-metal nitrides. An ab ini- into the metal lattice. The main thermodynamic facts we

0163-1829/93/48{16)/11685{7)/$06.00 48 11 685 1993 The American Physical Society

 J. HAGI. UND et aL

100 the interpretation of variations in L H.

E In the following analysis, we will study the formation
C)
of a NaCl structure compound MX &om the metallic el-
C$
1 ement in the fcc phase. Then we need the enthalpy dif-
O
ference between M in its stable structure at zero kelvin,
o SO —~ M~' ~, and in the fcc structure, M~ "~. Thus, we define
E
AE„,„,[M] = Et, [M( ")(a
6

)] —Et t [M(")],
7

where ao is the theoretical equilibrium lattice parame-

0 ter of M& "~, i.e. , the lattice parameter that minimizes
C4 E [M(' )]
We also want to separate out the efFect of volume
I changes in the formation of MX ' . The energy required
I I I I I
to expand M~ "& &om the theoretical equilibrium lattice
SC Ti V CI Mn Fe Co Ni parameter ao to the experimental (or estimated, see be-
FIG. 1. Enthalpies of formation b, H(TO) at To —298.15 low) lattice spacing a of the compound MX(' ) is
K from thermodynamic information for carbides of the
3d-transition metals. Curve 1 refers to carbides with the NaCl
[M(fcc) ( MA
)] E [M(fcc) ( M)]
structure while curves 2 —7 show b. H(To) values for complex (2)
carbides with compositions M3CQ M2C M7C3 M5C2 M3C,
and M23C6, respectively. Prom Ref. 4. Using the de6nitions above, the enthalpy of formation
per atom in the compound at zero kelvin can be written
want to account for are illustrated in Fig. 1. It shows the
enthalpy of formation, b. H(To) at To —298. 15 K, for 3d-
transition-metal carbides in the NaCl structure and for
A'H(0) [MX'"'] = AE,
1
.„, [MX'")]
1
several complex 3d-transition-metal carbides. Of partic-
+ bE.„,& [M] +— b, E„,„.[M]. —(3)
ular interest is the maximum in bonding strength for the
Here we have introduced a term that accounts for the
Ti carbides, the tendency for an almost constant H in 4 change in chemical bonding energy when carbon or ni-
the later part of the series, and the difFerence between the
trogen atoms are inserted into the metal fcc lattice while
NaC1 structure carbides and those having more complex
keeping the lattice parameter constant,
structures.
In Sec. II we
KEb „q[MX(")] = —(E, [MX(")] —E, , [M( ")(aM )]
Our paper is organized as follows.
consider the NaCl structure compounds. The relevant 2
thermodynamic quantities are defined, and results from
LMTO band-structure calculations are presented. In
.
-E. .[x(")] &. (4)
Sec. III we interpret these ab initio results in terms of This quantity has contributions &om M-X interactions,
a simple model that accounts for hybridization efFects. as well as &om changes in M-M bonding energies.
Section IV contains a discussion of the bonding proper- AEb „g[MX ' ] will be used in Sec. III for a discussion
ties of complex carbides and nitrides. The paper ends of hybridization and band-filling efFects in NaCl structure
with conclusions in Sec. V. transition-metal carbides and nitrides.

II. (cF8) NaC1-STRUCTURE COMPOUNDS

A. Thermodynamic de6nitions
Experimental information on bonding energies of solid
compounds is generally expressed as enthalpies of forma-
tion (boH) (cf. Fig. 1). This quantity represents the
energy gained in forming a compound (e.g. , MX, with
X=C,N) from the constituent elements in their stable
(st) modifications M(' ) and X(' ) at some reference tem-
perature. Usually, this corresponds to metals in a certain
crystal structure (e.g. , bcc, fcc, or hcp), carbon in the
graphite form and nitrogen as a diatomic gas [N2(g)]. In
this work, the reference states of carbon and nitrogen
are unimportant. In analogy with our previous works,
we therefore choose the &ee carbon and nitrogen atoms
C~ ~ and N~ as reference states. This choice corre-
~ dynamic information. However, what is relevant for the
sponds to a constant shift in A H and it does not afFect
B. A. b initio results
Following the definitions in Sec. IIA, we have cal-
„,
culated b, E,„&g[M] and bE, t, , [M] using the LMTO
method. Our version relies on the semirelativistic and
mufBn-tin-potential approximations. The present cal-
culations were all carried out with the Gunnarsson-
Lundqvist density-functional parametrization. Figure 2
„,
shows AE, t, [M) for the 3d-, 4d-, and 5d-transition met-
als discussed in this work. We note that the largest en-
thalpy difFerences are found among the elements that are
stable in the bcc structure at zero kelvin, i.e. , V, Cr, Fe,
Nb, Mo, Ta, and W. Except for Fe, these difFerences are
positive, as expected, but they are much larger in mag-
nitude than what is obtained by analyzing thermo-
present study is that bE, t,,„,[M] is much smaller in mag-
48 THEORY OF BONDING IN TRANSITION-METAL CARBIDES. . . 11 687

50 I I I I I I I
TABLE I. Ab initio calculated equilibrium lattice parame-
ters ao" of 3d-, 4d- and 5d-transition metals in the fcc struc-
40— —
---
3d
4d
ture.
.--- 5d (f~c) (fee) (ace)
30— ao ao ao
(a.u. ) (a.u. ) (a.u. )
E 20— Sc 8.55 Y 9.40 La 10.05
Tl 7.68 Zr 8.52 Hf 8.39
g 10— V 7.16 Nb 8.00 Ta 7.98
Cr 6.81 Mo 7.61 W 7.67
0— Mn 6.59 Tc 7.37 Re 7.46
Fe 6.49 Ru 7.24 Os 7.36
10 I I I I I I I I
Co 6.46 Rh 7.24 Ir 7.37
Sc Ti V Cr Mn Fe Co Ni
Y Zr Nb Mo Tc Ru Rh Pd
Ni 6.53 Pd 7.37 pt 7.50
La Hf Ta W Re Os Ir Pt

FIG. 2. Calculated structural enthalpy differences

AE, &,„,[M] for 3d-, 4d-, and 5d-transition metals [cf. Eq. (1)].
nitude than the variations in A H(0) (Fig. 3). Thus, the
fact that the stable structure of the transition metals at
zero kelvin changes along the Periodic Table can only ac-
count for a small or negligible part of the variation in
the total enthalpy of formation of their NaCl structure
compounds.
The equilibrium lattice parameters ao for all tran-
sition metals in the fcc structure are listed in Table I.
These values were obtained by Gtting a Murnaghan equa-
tion of state to total-energy results from LMTO band-
structure calculations. The lattice parameters a of
the carbides and nitrides studied in this paper are listed
in Refs. 1—3. All a refer to the stoichiometric compo-
sition of MX.
The volume expansion energies AE, „pg[M], defined in
Eq. (2), are plotted in Fig. 4. We find that AE, „~~[M]
has almost the same behavior in all three transition
metal series, with a maximum in their later parts. This
is understood by noting that AE, „~g[M] approximately
equals the product of the bulk modulus and the square
of the volume expansion. The calculated variation of
these quantities is shown in Fig. 5. The magnitude of
AE, „~d[M] is smaller in the 4d and 5d series than in the
3d series. This reQects the larger di8'erence between ao
and ao . Still, the variation of b, E,„~g[M] is relatively
small, compared with the variations in 4 H(0) (Fig. 3).

150—
400—
100—
300—
50-
200—
I I I I I I I I

Sc Ti V Cr Mn Fe Co Ni Sc Ti V Cr Mn Fe Co Ni

400— 50-
40-
300—
E
8 30-
200— N
20-
'K
100—
j0
I I I I I I

Y Zr Nb Mo Tc Ru Rh Pd Y Zr Nb Mo Tc Ru Rh Pd
I I

400— 30-
300— 20-
200—
10-
MN
100—
I I I I

La Hf Ta W Re Os Ir Pt La Hf Ta W Re Os Ir Pt

FIG. 3. Calculated enthalpies of formation at zero kelvin, FIG. 4. Calculated volume expansion energies AE „~s[M]
A H'(0), for 3d-, 4d-, and 5d-transition-metal carbides and for 3d-, 4d-, and 5d-transition metals [cf. Eq. (2)]. Note the
nitrides. different scales on the energy axis.
11 688 J. HAGLUND et al. 48

500
400 —
— 3d
4d
electronic states originate from carbon 8 electrons. No
significant electronic DOS is observed at the metal sites
~ --- 5d ~I

in this interval. The energy range that follows the carbon

300—
Q 8 band contains electronic states with both metal and
200— nonmetal character. The essential contributions come
100— from nonmetal p states and from metal d states, which
p 1 I
leads to the picture that hybridized p-d states dominate
the bonds between metal and nonmetal atoms. For sym-
60
5p — 3d
4d
metry reasons, there are metal d orbitals with small or
40— negligible overlap with carbon p orbitals. These states
30- contribute to metal-metal bonds in the compound.
Our results, based on a quantitative separation of con-
20-
tributions to A H(0) as expressed by Eq. (3), lead to
10—
the following picture for the bonding in NaCl structure
p I I I I

transition-metal carbides and nitrides. In the beginning

Sc Ti V Cr Mn Fe
Y Zr Nb Mo Tc Ru
La Hf Ta W Re Os
FIG. 5. Calculated bulk moduli K and volume difFerences
with respect to NaCl structure carbides and nitrides AV for
3d-, 4d-, and 5d-transition metals in the fcc structure.
III. INTERPRETATIONS
AND SIMPLE MODELS
The bonding in NaCl structure transition-metal car-
bides and nitrides has been studied previously by us
and by several other authors. For our discussion be-
low, we review the general behavior of the electronic en-
ergy spectrum in this class of compounds. Figure 6 shows
the electronic density of states (DOS) of FeC. It is com-
mon practice to consider atom and partial I projections
of the total density of states. For systems with more than
one type of atom, this separation is not unique since
it depends on how the crystal space is divided between
the different types of atoms. This is one reason why con-
siderations of projected DOS curves may be dificult or
misleading. However, Fig. 6 shows that the lowest-lying
Co Ni
Rh Pd of the transition-metal series, the Blling of bonding p-
Ir Pt
l hybridized states gives rise to maxima in the magni-
tude of AEb~„g for TiC, ZrC, and HfC (Fig. 7). Since
the structural enthalpy diff'erences AE, t, „,[M] and the
volume expansion energies b, E,„~g[M] are small, these
maxima are present also in b, oH(0) (Fig. 3). The nitro-
gen atom fills the electronic DOS with one more electron
than does the carbon atom. Within a rigid-band model,
this explains why the maximum bonding strength oc-
curs already at the first compounds in the series (ScN,
YN, and l.aN). This interpretation of the bonding in the
NaCl structure compounds formed by carbon or nitrogen
with metals in the erst part of the transition-metal series
agrees with that of most of the works cited above.
The decrease in E H(0) on going &om group V to VII
in the Periodic Table for the carbide series, and from
group IV to VI for the nitride series, is partly due to an
increased volume expansion term AE, „~g[M] in Eq. (3).
However, the major reason for the lowered enthalpy of
400—

I I I I

Total DOS I

MN
50.0— 200—

Sc Ti V Cr Mn Fe Co Ni
0.0
400-
O
50.0—
C4
300—
0.0 I
I
I

10.0—
I
I
200—
I
I

0.0 I

04 Fe s I
I
I
Y Zr Nb Mo Tc Ru Rh Pd
5, 0— I
I

0.0 400—
C p
10.0— 300—
0.0
20.0
0.0
-
~ C s

-0.2 0.0 0.2 0.4 0.6 0.8 1.0

Energy (Ry)
200—

100—
La Hf Ta W Re Os Ir Pt

FIG. 6. Calculated electronic density of states for FeC in FIG. 7. Calculated bonding energies —AE'b „g for 3d-, 4d-,
the NaCl structure. Note the difFerent scales on the DOS axis. and Sd-transition metals [cf. Eq. (4)].
48 THEORY OF BONDING IN TRANSITION-METAL CARBIDES. . .
formation is a decrease in the magnitude of LEb „g. This
is seen by comparing Figs. 3, 4, and 7. We conclude that
the electronic energy levels at the Fermi levels of these
compounds are best described as antibonding states.
For the compounds formed by metals in the last part
of the transition-metal series, the AoH(0) values from
our ab initio calculations remain almost constant, Fig. 3.
This trend is confirmed by our analysis of thermodynamic
information. The same slow variation is also present
in AEb~„g (Fig. 7) for the 4d- and 5d-series compounds,
while LEb „g in the later part of the 3d series shows a
slow decrease in magnitude. It is reasonable to describe
the electronic states being filled in these compounds as
nonbonding, since they do not increase the cohesive en-
ergy of the compound, relative to that of the pure metal.
It is possible that the different trend in the later part of
the 3d series is due to magnetic effects in these elements.
Figure 8 gives a schematic view of the bonding, antibond-
ing, and nonbonding character of the electronic DOS for
the present NaC1 structure compounds. Our model DOS
emphasizes the relatively low DOS values in the bonding
and antibonding regions compared with the large DOS in
the nonbonding energy range. This observation will be
used in the following section to qualitatively account for
some differences between the NaC1 structure compounds
and those with more complex crystal structure.
It should be remarked that there is no a priori rea-
son for the existence of a clean separation of the elec-
tronic energy spectrum into bonding, antibonding, and
nonbonding regions. Such a simplified view can only be
adopted if bonding energies, as in this case (Fig. 7), show
a clear pattern of variation. In contrast with the transi-
tion kom bonding to antibonding states, which often '
is connected with a well-defined minimum in the elec-
tronic DOS, the antibonding or nonbonding character of
the later part of the MX DOS (Fig. 6) cannot be eas-
ily distinguished. This is partly due to the ambiguous
separation of crystal space in atomic DOS projections
which, e.g. , may cause tails of metallic d orbitals to be
seen as nonmetal p states. A second complication is that
the bonding and antibonding states may be nonsymmet-
rically distributed on different types of atoms. Schwarz
MX
8 A N the reason why an ab initio calculation for alt of them
0A
M~X
B A N
Energy
FIG. 8. Schematic electronic densities of states illustrat-
ing the bonding (H), antibonding (A), and nonbonding (N)
character of difFerent energy regions in the energy spectrum
for NaC1 structure carbides and nitrides (upper curve) and
M3X compounds (lower curve).
11 689
has shown that the antibonding part of the p-d hybridized
states has strong metal d character while the nonmetal p
character is more pronounced in the bonding electronic
states. We suggest that this effect explains why only a
small nonmetal p contribution is seen in the antibonding
region of the DOS in NaCl structure MX compounds.
Gelatt, Williams, and Moruzzi focused on NaCl
structure transition-metal monoborides, as an example
of interstitial metal-nonmetal compounds, but AoH(0)
curves for NaC1 structure carbides and nitrides of the
4d-transition metals were also presented. Prom ab ini-
tio calculations of the enthalpy of formation, they con-
cluded that the decrease in the magnitude of 6 H(0)
in the middle of a transition-metal series (cf. Fig. 3) is
mainly a volume effect, i.e. , it reHects a loss of metal-
metal bonding energy as the metal expands to form a
metal-nonmetal compound. Moreover, they observed a
decrease in the magnitude of A H(0) towards the end
of the transition-metal series, which was explained as
due to the filling of antibonding p-d hybridized states.
Our interpretation of the variation in E H(0) for NaCl
structure compounds leads to a picture which is differ-
ent Rom that of Gelatt, Williams, and Moruzzi We
find that the decrease in the magnitude of b, H(0) in
the middle of the transition-metal series is mainly the
result of reduced chemical bonding, while volume effects
account only for a minor part of the variation. Further,
we observe an almost constant 4 H(0) in the last part of
the transition-metal series. In that region, KoH(0) ob-
tained by Gelatt, Williams, and Moruzzi decreases in
magnitude, which explains why they come to a different
conclusion regarding the bonding character of the states
in the upper part of the electronic energy spectrum.
IV. COMPLEX CARBIDES AND NITRIDES
We now turn to the complex carbides M3C2, M2C,
M7C3 MSC2) M3C, and M23C6. Many of them have
been studied experimentally, when M is a transition
metal in the later part of the 3d series. That enabled
us to derive4 the enthalpies of formation 6 H(To) which
are shown in Fig. 1. We shall now give an interpreta-
tion of variations in A H(To), based on the electronic
structure.
The large number of atoms per unit cell needed to de-
scribe the crystal structures of the complex carbides is
is not yet realistic. We have previously performed band-
structure calculations on Fe3C in its ferromagnetic state.
In the present discussion, we will partly invoke band-
filling arguments, and it is more relevant to consider Fe3C
in a nonmagnetic electronic configuration. The result-
ing DOS is shown in Fig. 9. We note that many of the
general features in the electronic DOS of NaCl structure
compounds (Fig. 6) are found also for FesC. For instance,
the lowest lying band is still of carbon s character and
well separated f'rom other states. Further, the dominant
contributions to the central part of the valence energy
spectrum come from carbon p states and metal d states.
There, we distinguish a low-energy part which contains
11 690 J. HAGLUND et al. 48

p-d hybridized states and a region which mostly consists Total DOS
of states with metal d character. An important differ- 400.0—
ence between the energy spectrum of Fe3C and that of
the NaCl structure compounds is that the DOS for M3C
200.0- I)
lacks the pronounced. structures that are seen in the DOS 0.0
Fed
I

I
I

of the MC compounds. This is qualitatively explained.

I

400.0—
I

by the lower lattice symmetry and the larger number of

atoms per crystallographic unit cell in the M3C com- 200.0—
pounds. CC
0.0
In our previous studies, we found that the DOS of all 400 Fe P
the transition-metal carbides of the NaCl crystal struc- rA
ture are very similar. Therefore we expect that our 0A
C/0
4p. p—
I

DOS for Fe3C is characteristic also of the other MSC

transition-metal compounds. Further, we assume that 00 n C I
I
%VX
1000 P I
I

the general differences found between the DOS of the I

I

NaCl (Fig. 6) and the Fes C structure compounds (Fig. 9) 0.0 I

100.0-
I
I

hold in a comparison with other complex transition-metal I

I
I

carbide s. 0.0 I I I g

We will now argue that many of the features of A H
in Fig. 1 can be understood in terms of our simplified
model DOS curves as in Fig. 8. Consider the first part
of the transition-metal series. The rise in the magni-
tude of L H in this region for NaCl structure carbides
was explained above as due to the filling of bonding, p-d
hybridized states. The same increase is seen for all com-
plex carbides. Since we showed that the DOS of Fe3C in
this energy range consists of hybridized p-d states, it is
reasonable to invoke the same explanation also for com-
plex carbides. We note that the broad minimum which
separates bonding and antibonding states in the DOS of
the NaC1 structure compounds is not present for Fe3C.
This leads to a smaller bandwidth and a larger average
DOS for the p-d hybridized region in FesC (cf. Fig. 8)
and thus to a smaller energy gain associated with filled
bonding p-d hybridized states. A second factor which
afFects the increase in the magnitude of L H is the rel-
ative carbon (or nitrogen) content of the compound. A
lower nonmetal concentration will lead to fewer metal-
nonmetal bonds and thus to a lower energy associated
with these bonds. This agrees well with the sequence of
L H curves for complex carbides in Fig. 1.
In analogy to what was concluded for the NaCl struc-
ture compounds, we suggest that the decrease in the mag-
nitude of 4 H for the complex systems in the middle of
the transition-metal series is due to the filling of anti-
bonding states; cf. Fig. 8. This decrease is more pro-
nounced for NaCl structure compounds, since the lower
DOS in this energy range implies a population of higher
energy states. Finally, the almost constant behavior of
A H in the last part of the transition-metal series agrees
well with the 611ing of nonbonding states. However, one
should note that the L H values in this energy region
depend on the position of the nonbonding region in the
energy spectrum. Thus, if the nonbonding DOS is dis-
placed towards higher energies for NaCl structure com-
pounds than for complex carbides and nitrides, as illus-
trated in Fig. 8, the magnitude of the corresponding4 H The bonding and antibonding states are formed by hy-
will be lower. We suggest that this is the main reason
why the A H(TO) curves for the complex carbides and
the NaCl structure carbides tend to different values in
the later part of the transition-metal series (Fig. 1).
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
Energy (Ry)
FIG. 9. Calculated electronic density of states for nonmag-
netic Fe3C. Note the diferent scales on the DOS axis.
Thermodynamic data on 4
H for some stable com-
plex 3d-transition-metal nitrides show the same qualita-
tive behavior as for the corresponding carbides. In view
of the similarities in the electronic structures of the NaCl
structure carbides and nitrides of the 3d series, we expect
that the interpretation above of the bonding in complex
3d-transition-metal carbides can be extended to the ni-
trides. Likewise, we expect complex carbides and nitrides
formed by 4d- and 5d-transition metals to follow the same
pattern.
V. CONCLUSIONS
The purpose of this paper has been to increase the un-
derstanding of bonding in transition-metal carbides and
nitrides. Our discussion is based on total energies &om
ab initio electron-structure calculations. Since ab initio
results are known to have significant absolute errors, we
have in previous works critically compared them with
thermodynamic information. We conclude &om those
works that ab initio results on enthalpies of formation
4 H and cohesive energies E, g are adequate for the
present analysis of the trends in bonding energies.
We have studied in detail the 3d-, 4d-, and 5d-
transition-metal carbides and nitrides in the NaCl crystal
structure. It is found that L H for the carbides has a
characteristic variation along a d series, with an initial in-
crease to a maximum, followed by a d.ecrease and then an
almost constant value. These three regions can be given
a simple interpretation in terms of the successive Ailing
of bonding, antibonding, and nonbonding electron states.
bridized carbon p states and metal d states, i.e. , they
correspond to metal-nonmetal bonds. The nonbonding
part of the electronic energy spectrum is dominated by
metal d states, corresponding to metal-metal bonds.
 48 THEORY OF BONDING IN TRANSITION-METAL CARBIDES. . .
When an interstitial compound is formed &om the con-
stituent elements, one is led to consider the influence on
L H &om differences in the atomic size and in the struc-
tural enthalpy for the pure elements. We And that these
effects are of little importance for the overall variation in
4 H along the transition-metal series.
Transition metals M may form a large number of
compounds having crystal structures more complex than
NaCl, e.g. , with compositions M3C2 M2C, MyC3 M5C2,
M3C, and M23C6. There is ample evidence that L H
for such systems has a behavior along a transition-metal
series similar to that of the NaCl compounds, but with a
less pronounced maximum. We suggest that the general
pattern of variation in 4 H can be understood within the
same picture of bonding, antibonding, and nonbonding
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11 691
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of metal-nonmetal bonds.
ACKNOW LEDGMENTS
This work was supported by The Swedish National
Board for Industrial and Technical Development, The
Swedish Research Council for Engineering Sciences, The
Swedish Natural Sciences Research Council, and The
Goran Gustafsson Foundation.
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