PERSPECTIVES ammmmommmm'II .

11",owmmmm- -mom= amm a w--

1-M M-,

Mechanochemistry rises, but the LUMO-HOMO gap decreases,

and so the internal stability decreases. As a
result, there is a greater opportunity for
John J. Gilman chemical reactions to take place. If a mol-
ecule is bent in its ground state, straightening
it decreases its stability.
In periodic solids (crystals), the equiva-
lents of LUMO-HOMO gaps are band gaps.
Chemical reactions can be triggered by me- Mechanochemical effects have often Bonding orbitals correspond to valence
chanical forces in solids because, unlike gases been attributed to strain energy assisting bands; and antibonding orbitals, to conduc-
and liquids, solids support shear strains. thermal energy. However, at low tempera- tion bands. The larger the band gap, the
Shear changes the symmetry ofa molecule or tures, the strain energy density may be larger more stable the crystal structure (6). For ex-
solid and is therefore more effective in stimu- than the thermal energy density, so this as- ample, there are two mechanical paths for
lating reactions than is simple isotropic com- sumption is inappropriate. In many cases, converting insulators into metals. One, the
pression. Sheared spheres become ellipsoids, dislocation motion concentrates the applied Herzfeld-Mott approach (7), reduces dis-
cubic symmetry becomes tetragonal, and so strain, creating large local strains (5). tances between atoms so that the overlaps of
on. Such symmetry breaking destabilizes the When covalent bonds are bent (sheared), their wave functions increase. The other
electronic structure of bonding and makes the energies of their highest occupied mo- changes the bond angles through shear,
the solid prone to chemical reaction. Such lecular orbitals (HOMOs) are raised, thereby reducing the minimum band gap (8).
mechanochemical phenomena A simple two-dimensional model that
are found in a variety of pro- Antibonding compares the effects of shear versus isotropic
cesses-friction and wear, deto- compression on the electronic structure pro-
p iii
LUMO_ vides some insight (9). By shortening one
nations, solid-state synthesis, and
mechanical alloying. axis while lengthening the other, shear shifts
Boldyrev (1) has emphasized two band gaps oppositely in energy, whereas
that products of mechanochemi- Nonbonding , isotropic compression shifts them in the same
cal reactions may be distinct from D HOMO t||| direction. Thus, the minimum (indirect) gap
those of thermochemical ones for is decreased by shear but is nearly unchanged
the same reactants. Until re- by isotropic compression. Band structure
cently, there was a great deal of computations of 3D molecules are consistent
phenomenological knowledge in Bonding with this simple model (10).
this field but no satisfactory When the strain becomes large enough
knowledge of mechanisms. 4 to close the gap, the bonding electrons can
Bridgman (2) reported in 1935 move freely, so that a transformation, or
that he could cause a variety of reaction, can proceed athermally. In inter-
chemical changes by applying a Straight F Strain > Bent mediate cases, the electronic process may
combination of axial compres- How straiiin triggers chemical reactions. Walsh energy-level be assisted by phonons, allowing reactions
sion and torsion to specimens diagram ffor H- showing the effect of bending shear on the to occur very rapidly at low temperatures
held between two "Bridgman an- LUMO-HC )MO gap. Occupation of the levels is indicated by the because of its electronic basis. Mechanochem-
vils" at room temperature. Under small arro)ws, which represent spin-up and spin-down elec- istry is especially important for ultrafast re-
about 50 kbar of compression trons. Thet,tronic ,re are three protons and four electrons. The phases actions, as in explosive shock fronts. It ac-
(plus torsion), he could cross-link of the elec-ed for wave functions are indicated as yellow for 0 0
=
counts for the transitions between deflagra-
with like phases bond; unlike
polymers, decompose compounds ones antibDond. Mixed Neighbors
and as re( =
(half-shaded) ones do neither. tions that travel at sonic speeds and detona-
such as PbO and KMnO4, and tions that travel supersonically through a
drive substitution reactions such as 2AI + whereas the energies of their lowest unoccu- solid. The former are thermally activated,
Fe2O3 -* A1203 + 2Fe and Mg + SiO2 -* pied molecular orbitals (LUMOs) are low- whereas the latter are athermal ( 1).
MgO + Si. Because his specimens were thin ered. Thus, the gap between these levels,
wafers and his anvils were good thermal con- which determines a bond's stability, is de- References
ductors, he concluded that the reactions creased (6). This may be viewed as an inverse
were athermal. Jahn-Teller effect. 1. V. V. Boldyrev, J. Chim. Phys. 83, 821 (1986).
Enikolopyan et al. (3) extended Bridg- Consider the simplest case: the hypotheti- 2. P. W. Bridgman, Phys. Rev. 48, 825 (1935).
N. S. Enikolopyan et al., Dokl. Akad. Nauk SSSR
man's work to various inorganic compounds, cal H; molecule, which is related to the azide 3. 292,1165(1987).
such as hydrated cupric sulfate, and to the ion N-. A Walsh diagram indicates the mo- 4. A. A. Zharov, in High Pressure Chemistry and
polymerization of various organic monomers lecular orbital energy as a function of bond Physics of Polymers, A. L. Kovarskii, Ed. (CRC
(those containing -C=C-, -C=N-, C_C, angle (see figure). Such a diagram shows that 5. Press, Boca Raton, FL, 1994), chap. 7.
R. W. Armstrong, C. S. Coffey, W. L. Elban, in
C=C=C, and heterocyclic and aromatic like pairs with in-phase wave functions form Advances in Chemical Reaction Dynamics, P.
groups). Hundreds of such mechano-reac- bonds, whereas unlike pairs form antibonds. Rentzepis and C. Capellos, Eds. (Reidel, Dordrecht,
tions are reviewed by Zharov (4). Studies of For the bent molecule on the right, the Netherlands, 1986), p. 486.
acrylamide have demonstrated that polymer- lowest orbital (bonding orbital) is stabilized 6. J.Univ. K. Burdett, Chemical Bonding in Solids (Oxford
Press, New York, 1995), chap. 8.
ization occurs principally during the shear by increased bonding between the two end 7. P. P. Edwards, T. V. Ramakrishnan, C. N. R. Rao,
deformation, not afterwards. atoms. This interaction increases for the Eds., Metal-Insulator Transitions Revisited (Taylor
antibonding orbital, thereby lowering its en- & Francis, London, 1995) p. xv.
ergy, and decreases for the nonbonding or-
8. J. J. Gilman, Philos. Mag. B 67, 207 (1993).
The author is in the Department of Materia ils Science 9. Czech. J. Phys. 45, 913 (1995).
and Engineering, University of California, Lc)s Angeles, bital, so its energy increases. Work is done on 10. A. B. Kunz, Mat. Res. Soc. Symp. 418, 287 (1996).
CA 90095-1595, USA. the molecule to bend it, thus the total energy 11. J. J. Gilman, Philos. Mag. B71, 1057 (1995).
SCIENCE * VOL. 274 * 4 OCTOBER 1996 65