Anerican Min*olooist Vol. 57, pp.

t57S-1613 (J922')

CORR.ELATIONS BETWEEN Si_O BOND LENGTH, Si-O-Si ANGLE AND BOND OVERLAP POPULATTONS CALCULATED USING EXTENDED HUCKEL MOLECULAR ORBITAL THEORY G. V. Gmns,M. M. Hernr,l aNDS. J. LoqrsxlrHaN, D ep'artmentof Geoto'Eiaa.l Sciences, Virginia Polytechnic Institute ond State Uniuersitg, B lacksburg, Vir girui,a I 2406
AND

L. S. Benrcr,r, ANDHsruKANcYow, D epartnzentof Ch,emistrg, Uniu ersity o,f Miehig an, Arm,Arbor, Miahigo"n4810! AssrRecr
Extended Htickel molecr:lar orbital calculations have bee=n completed fof isolated and polymerized tetrahedral ions for ten bilicate mineral! in which a(O) s 0.0 using ob.servedO-Si-O and Si-O-Si valence angles, assuming all Si-O bond lengths are 1.63A and including silicon 3s and 3p and oxygen 2s and.2p i,tdmic orbitals as the basis set. The resultant Mulliken bond overlap populations, z(Si-O),,correlate with observed Si-O bond lengths, the shorter bonds being associated with the larger n(Si-O). If the five Si(3d) atomic orbitals are also included in the basis set, the observedSi-O(br) and Si-O(nbr) bond lengths correlate with n (Si-O) as two separate trends with overlap populations for the Si-O(nbr) bonds exceedingthose for Si-O(br) by about 20 percent, even if the Si-O-Si angle is 180o. Calculation of z(Si-O) as q function of the Si-O-Si angle for the Si-O bo"ds irr Sir6ro- (assuming Si-O : 1.634 and { G-Si-O : 109.47o)first excluding and then including the 3d-orbitals, predicts in each case that the Si-O(br) bond lengths should decreasenon-linearly and that the Si-O(nbr) bond lengths should increase slightly as the Si-G-Si angle increases. Scatter diagrams of observed Si-O(br) bond lengths to two-coordinated oxygens versus the Si-O-Si angle appear to va,ry non-linearly with the shorter bonds tending to occur at wider angles.If these bond lengths a,rereplotted against - 1/cos(Si-O-Si), the scatter diagrams show improved linear trends. Multiple linear and stepwise regression analyses of the bond lengths as a function of -1/cos(Si-O-Si), Af(O) and (CN) indicate that each makes a significant contribution to the variance of the Si-O(br) bond length. The conclusion by Baur (1971) that the Si-O(br) bond length is independent of Si-O-Si angle in silicates for which Af(O) : 0.0 can be rejected at the 99 percent confidence level.

IwrnonucnoN Pauling (1939) has concluded difference from the electronegativity between Si and O that the Si-O o--bond has about 50 percent ionic
l Now at the Geology Department, Rutgers-The Brunswick, New Jersey 08903. State University, New

1578

MO CALCULATIONS FOE SILICATE IONS

1579

character, attributing a charge of about '*2 on the silicon atom. Becausethis charge exceeds*1, thereby violating his electroneutrality principle, he (1952) postulatedthe formation of.d-p.-bonds betweenthe two atoms to neutralizethe charge.Using an empirical equatio r relating interatornic distanceto the amount of char"'-bond acter, he then computeda Si-O distanceof 1.63Ain closeagreement with reported values. Subsequently, Fyfe (1954) calculated semiempirical bond energies for the SiO+tetrahedronas a function of the Si-O separation,and concludedthat the relatively short Si-O bond can be explainedwithout resorting to extensivedouble bonding.On the other hand, Cruickshank (1961) has assertedon the basis of group-theoretic arguments,approximate molecular orbital calculations, and group overlap integralstha;t of the five 3d-orbitals, only the two e orbitals on silicon form strong z'-bondswith the appropriate 2pr lone pair orbitals on oxygen.The Si(3d) orbital involvementin the Si-O bond has since been substantiated by all-electron a,birui.tio SCF molecularorbital calculationsfor the silicate ion and orthosilicic acid (Collins, Cruickshank, and Breeze, lg72). These calculations show (1) that there is considerable Si(3d,)-orbital participation in the wavefunctions with the e orbitals forming and the f2 "'-bonds orbitals forming o-bonds with the appropriate valence orbitals on oxygen; (2) that the calculatedl"e,sX-ray fluorescence spectrausing Sd-orbitals are in remarkably good agreement with the experimental spectra of silica glass; the agreementis notably poorer when the 3d-orbitals are not included in the calculation (seeFig. 1); and (3) that the residualchargeon Si is not *4 as assumed in an electrostatic modelbut is closeto zeroin reasonable agreement with Pauling's principle and the resultsof a Si(K)-spectrochemical electroneutrality shift study by Urusov (1967). Within the last decade a large number of silicate and siloxane structures have been carefully refined using precise difiraction data obtained by modern techniques. These refinements have revealed a numbet of systematic variations in bond lengths and bond angles: (1) the Si-O(nbr) bonds are usually shorter than the Si-O(br) bonds; (2) shorter Si-O bonds are usually involved in wider O-Si-O and Si-O-Si angles;and (3) the tetrahedral anglesusually decrease in the order d [o (nbr)-Si-o (nbr)] > { [O(nbr)-Si-O@r)] > { [o (br)-Si-o(br)]. Several investigators have arg ed that these variations can be rationalized in terms of a covalent m del that includes3d-orbital involvement between silicon and oxygen cl. Cruickshank, 1961; Lazarev, 1964;

GIBBg, HAMTL, T,OUISNATHAN,BARTELL, AND YOW

Frc. 1. Comparison of (q) the experimental L." X-raY fluspectra for silica"glass orescence with that calculated by Collins et aI, (1972) from rmults obtained in all-electron ab ini'tin SFC MO calculations on the silicate ion (b) using an extended basis set that includes Si(3d) orbitals and (c) using a minimum basis set that excludes Si(3d) orbitals.

E,

o
o

F (J lrJ F lrJ ltJ I F F

UJ UJ (J lrj E. a F

z l o ()
l!

o o z

MO CALCULATIONSFOR SILICATE IONS

1581

McDonald and Cruickshank, 1967a; Cannillo, Rossi, and Ungaretti, 1968;Bokii and Struchkov,1968;Noll, 1968;Brown, Gibbs,and Ribbe, 1969;Brown and Gibbs, 1970;Louisnathan and Smith, 1971;Mitchell, Bloss,and Gibbs, 1971).On the other hand, consistency with a covalent model that includes3d-orbital involvement doesnot, of course,preclude other bonding models. For example, Mitchell (1969) notes that the sametrends are implicit both in Gillespie's(1960)valence-shellelectronpair repulsion model and in a molecular orbital model involving a valence basis set of atomic orbitals (without the 3d-orbitals of Si). Despite the systematic variations observed between Si-O bond length and the Si-O-Si and O-Si-O anglesin silicatesand siloxanes, no attempt has yet beenmade to rationalizethesetrends in terms of modernvalencetheory. An attempt at such a classification shouldnot only serve to improve our understanding and interpretation of such observables as the elasticconstants(Wiednerand Simmons, 1972),the bond polarizabiliiies (Revesz,1977) susceptibilities the diamagnetic , (Verhoogen, 1958), the Raman and infrared spectra (Griffith, 1969) and the X-ray emissionand fluorescence spectra (Dodd and Glen, 1969;Urch,1969;Collinset a1.,1972) in general butshould of silicates also clarify our understandingof the long-range and short-range forces involved in A/Si ordering (Stewart and Ribbe, 1969; Brown and Gibbs,1970). Recently,Baur (1970,1971)attempted to rationalizethe Si-O bond length variations for a large number of silicatesin terms of an electrostatic model by showing that the Si-O bond lengths predicted by his so-called extended electrostatic valence rule correlate well with those observed for structures where LfQ) + 0'. However, he notes that the rule fails to predict bond length variations in silicateslike quartz and forsterite where Af(O) : 0.0. In spite of this shortcoming,Baur has rejected Cruickshank'sdoublebonding model in favor of an electrostatic
I For Si-O bond length variations in the tetrahedral portion of a silicate, the extended electroStatic valence nrle states that the deviation of an individual Si-O bond from the mean tength, (Si-O), in a silicate ion is proportional to Af(O). The actual bond length is predicted by the empirical equation Si-op*a. : (si-o) + 0.091 ^f(o) where af(O) : f(O) - f(O), l(O) is the sum of the Pauling (1929; 1960)bond strengths received by oxygen andf(O) is the mean f(O) for the silicate ion under consideration.Baur (1970, 1971) usesp6 instead of f(O) to denote the sum of the bond strengths received by oxygen. However, we prefer to retain Pauling's symbolism for two reasons: (1) f(O) is an accepted symbol used by many investigators and (2) p denotes bond-order or bond-number in modern valence theory (c/. Coulson, 1939; Pople el al., 1965; and Mulliken, 1955).

T582

GIBBS,, HAMIL, LOUISNATHAN,,BARTELL, AND YOW

model (l) becduse prouea dependence he could r;Lot betweenSi-O bond

suggeststhat irnoreof the variation in bond length may be explained in terms of Af(O) than in terms of the angle, it cannot be concluded a priori that fhe bond length variation is independent of the angle without appropriatestatistical tests. Accordingto Baur (1971),the main difference betweenhis electrostatic model and Cruickshank'sdouble bonding model is that the latter stressesthe importance of the intrinsic electronic structure of the tetrahedral ions whereas his electrostatic model stressesthe extrinsic effects from the the non-tetrahedral cations. Although Baur is aware of the empirical nature of his model and the fact that it cerbainly cannot replace a model basedon electronic structure, he has stated that future models for the Si-O bond (1) should incorporate the electronic structure of the constituent atoms as well as the effects of the non-tetrahedralcationsand (2) shouldbeginwherehis electrostatic model breaks down (for minerals like forsterile, quarbz, etc.). The Si-O bond length variations in forsterite were recently examined in terms of extendedHiickel molecular orbital (EIIMO) theory by Louisnathan and Gibbs (1971) who found that the observedbond length variations show a close correspondence with bond overlap populations,n(Si-O), calculated (1) for the silicate ion alone and (2) for the silicate ion with its nearest neighbor non-tetrahedral cationsand their ligands.

r T'he relationship between Si-O distance and Si-O-Si ahgle for the silica polymorphs was recently re-examined by D. Taylor (lWZ); SeeMineral.:' Mag. 38, 62H31. After correcting the $i-O distances in the polymorphs for thermal motion of the oxygen atoms, Taylor calsulated a regression line for the corrected Si-O bond lengths and their associated Si-O-Si angles. Ile found the resulting line to be less steep than those calculated earlier by Brown et aI. (1969) for the framework silicates but statistically identical to the one calculated in. our study (see Table 3). Moreover, Taylor notes the probability the slope of the line might be zero is a little less than 0.05, a result at va.riance with the findings by Baur (1971) who believes that a dependence between Si-O distance and Si-O-Si angles does not exist for minerals like the silica polymorphs where Af(O) - 0.0.

MO CALCULATIONS FOR SILICATE IONS ??(Si-O)calculatedwith Si(spd) valencebasis set for the silicate ion in forsterite

1583

(1) For the silicate ion (2) With non-tetrahedral alone cations and their ligands Bond Length Si-O(1) : 1.6134 Si-O(2) : 1.654 Si-O(3) : 1.635

n(Si-O) 0.935 0.878 0.892

n (Si-O) 1.003 0.931 0.968

The n(Si-O) calculatedfor the silica;te ion alone (seecol. l above) were made using the observedO-Si-O angles but with all Si-O distances set equal to 1.634. Despite the assumptionin the carculation that all si-o bond lengths are constant, it is clear that the resurting n.(Si-O) can be used to order the observedSi-O bond lengths in forsterite. Encouraged by this result, the present study was undertaken to learn whetheror not EHMO theory can serveas a model for classifyingand ordering si-o bond length variations when the nontetrahedral cations are ignored and a((O)=0.0'. Moreover, in the event that these calculationsprove successful, they should improve o'ur understandingof the nature of the si-o bond in terms of modern valence theory and provide plausible reasonsfor the variation of individual si-o bond lengthsin silicatesand siloxanes in generar. rn addition,new scatterdiagramsof si-o (br) bond lengthplotted against Si-O-Si angle will be presented for data from Bl carefully refined silicate and several siloxane structures in which A((O) is zero or small.The relative contributionsof Si-O-Si, -l/cos(Si-O-Si), A((O), and (CN) (the mean coordination number of oxygen bonded to silicon) to the Si-O(br) bond length in these structureswill be assessedusing multiple linear and stepwiseregression methodsl (see appendix).The outcomeof the analysiswill show that we can reject the hypothesis that a relationshipbetween Si-O(br) and Si-O-Si angle might not exist for silicateswhereA((O) = 0.0. Trrn Cer,cur,ATroN emn SrcNrrrcANcE or Boxl Ovnnr,epporur,lrroys Osrarxnu rN THEExruxopn Hiicrnr, Mor,ncur,enOnsrrAr,Trrrony SincePauling (1929) formulatedhis famousset of rules for predicting stable atom configurations in ionic crystals,many silicate structures haVe been investigated by X-ray methods and have been found
'Linear, multiple linear, and stepwise linear regression computations presented in our paper were completed using the UCLA BIOMEDICAL PROGRAM PACKAGE,1967.

1584

BABTELL,AND YO'W GIBBS,HAMIL, LOUISNATHAN,

the steric details of the to conform remarkably well. Nevertheless, tetrahedral ions in many of thesesame silicatesalso appearto conform with a model that includescovalentbonding (cf. Brown et al', 1969;Brown and Gibbs, 1970).In an attempt to learn whetherthese details are indeed consistentwith covalent theory, extendedHiickel molecular orbital calculationswere made for the tetrahedral ions in suchthat A((O) is either zero ten silicatemineralsspecificallychosen or small. In this way the importanceof the intrinsic electronicstructo the reader (Hamil, ture of the tetrahedral ions can be emphasized Gibbs,Bartell and Yow, 1971).Silicatesshowinga larger variation in by Louisnathanand Gibbs in a elsewhere a((O) will be considered (1972d). calculations,although very EHMO the disilicates study of inexpensive and crude by ab initio'standards(Richardsand Horsley, Walsh-Mulliken in generating 1970),have beenmoderatelysuccessful bond angle) plotted against (molecular energies orbital diagrams (c/. Hoffmann, 1963; Gavin, 1969; Allen, 1970; 1972) and' in delineating trends in variations of bond length with bond overlap popuin lations or bond.order for a number of relatively large molecules Boyd 1969; 1968; Gavin, (c'1. ground and Ross, Dallinga states their and Lipscomb, 1969). Recently, Bartell, Su, and Yow (1970) calculated EHMO bond overlap populationsfor the tetrahedral bonds in selectedsulfates and phosphatesand found that they show strong correlationswith (1) the simple valence bond orders assignedby Cruickshank (1961) and (2) the observedtetrahedral bond lengths' To learn whethersi-o bond overlappopulationsfor the silicatesshow similar trends, calculationswere undertaken using an EHMO proonegram originally written by Hoffmann (1963).In the calculations, combilinear as a electronmolecularorbitals, MOs, are constructed nation of atomic orbitals,LCAO,

vo : t, co,6,
where c16i &r-the linear .oum.i.ot.- und 41 the Slater type single exponent atomic valence orbitals. The energy associated with an MO, - .Stil = ea,is obtained by diagonalizing the secular determinant lHot (explicitly evaluated 0, where Sri are the two center overlap integrals from the positional coordinates of the constituent atoms) , a,nd'Hai a're the elements of the Hiickel Hamiltonian matrix. In the rigorous Roothaan-Hartree,Fock method, the Ha1are complicated functions of the linear coefficients and of two-, three-, and four-centered integrals, and this fact requires an iterative solution of the secular equation (Richards and Horsley, 1970). On the other hand, in EHMO theory

MO CALCULATIONS FOR SILICATE IONS

1585

lhe H15 terms are not explicitly evaluated but are chosento simulate spectroscopically obtained quantities, namely the negative of the valence orbital ionization potentials (VOIP) whereasthe I/ai terms are approximated by the Wolfsberg-Helmholz(1952)parametrization Htr:Bno(//',*H,,). When one-electron MOs are constructed obtained, and their energies the Pauli exclusion principle is applied as an afterthought and the MOs are filled with electrons pair-wise starbing from the lowest eigenstate. By inserbingeigenvalues, e;,,into the set of secularequations, i : o, (t,o - els;;)c6,.

the linear coefficientscpi &ra evaluated but they are not in any way refined to self-consistency. It is important to note that trends in these linear coefficients dependin large part on the geometryof the tetrahedral ions modeledin our calculations. Finally, a Mulliken (1955) population analysis is cornpletedto obtain the desiredSi-O bond overlap populations, n(Si-o) : 2 X N(/r) t I co,coiS,i,

using the overlap integrals, ,ri. ,rrr"urt"to"*lr"n* and the number of electrons, ff(k), (0, 1, or 2) in MO rI,7,. The bond overlap populations provide numdrical estimates of the strength of covalent bonding and anti-bonding betweentwo atoms. Two atoms are considered to be bondedwhen the overlappopulationis positive,nonbonded when it is zero, and antibonded when it is negativel short bonds are usually involvedwith large overlappopulationsand longerbondswith smaller ones.If observedSi-O bond lengths are used in the calculation of n.(Si-O),the shorterbonds, which usually have largeroverlapintegrals, S,;y, will tend to have larger bond overlap populat'ionsthan longer bonds. As it is important to be able to discriminate betweenthis induced correlationand that inducedby the geometrical aspects of the tetrahedral ions, we have undertakentwo separatecalculations (1) using the observed O-Si-O and Si-O-Si anglesand clampingall Si-O distancesat 1.634 and (2) using the observeddistancesand angles. By clamping all the Si-O at 1.&34,the correlationbetweenz(Si-O) and the observedSi-O bond length induced by the overlap integrals is effectively removed and what remains should be related to the intrinsic electronic structure of the ions induced in large part by such

1586

BARTELL, AND YOW GIBBS;HAM'IL, LOIIISNATHAN,

of the Because geometrical factors as the o-si-o and si-o-si angles. very crude nature of the EHMO method intrinsic in'the very daring of the utter neglectof the outlined aboveand because approximations interacpotential producedby the cotilomb and exchange screening obtained nu,rnbers !,o actual' Lhe attached be can tions, little significance ra(si-o) the calculated for zr,(si-o). However,it is the trends between ale conthat lengths bond si-o determined and the exp,erimentally tetrahedral one any for numbers absolute sideredsignificant,not the ion. Thus, EHMO results can be useful in ordering and cl'assifging bond lengthswith bond overlappopulationsbut it cannotbe observed used to proue the observedbond length variations nor can it be used Lo pt'o,ue the participation of the 3d-orbitals of si in the wave functions for the ions studied. calculated The YOIP and orbital exponentsused as input to the program are given in Table 1. For the s- and p- orbitals the free-atorn optimized orbital exponentsof clementi and Raimondi (1963) were chosen together with voIP similar to the zero-chargevalues of Basch, viste, uoa Gruy (1965). For the 3d orbitals of silicon, an orbital exponent significantly higher than the Slater-rule value was adoptedfor reasons was adjustedto -5'5 eV H,s6,sa by Bartell et al,.(1970), and' discussed in the caseof to yield orbital and overlap populationscomparable, (1969)' Lipscomb SiHa, to ab ini'tio populationsfound by Boer and out to turned Theseparametersgave 3d populationsin sio+* which be of the same magnitude as Lheab initio poptiations reporbedsubby Collins e'tal. (1972). sequently A fundamental weaknessof the extendedHiickel scheme(which is not based on u b.ormfi'd,eHam\ltonian) is that its energiesand wave functions are sensitive t0 the somewhat arbitrary parameterization On the have only a qualitative significance. adoptedand, accordingly, other hand, the EHMO trendsin chargedistributionsand bond popuT.cnr,n 1. Ver,pNcp Onsrrer, Ioxrzerron PornNtrar,s (VOIP) eNo OnsttaL ExpoNprrs (). $tom Oxygen

Atomic Orbital 2s 2p

VOIP (eV) -32.33 -r5.79 - 14.19 -8 .15 2.246 2.227 1.634 t.428

Silicon

.JS

3p

MO CALCALATIONS FOE SILICATE IONS

1587

lations in a seriesof related moleculeshave been found to be insensitiveto the exact parameterization; they are also roughly independent of whether the VOIP are frozen at plausiblevalues or &re adjusted to self-consistencywith aiornic charges (Basch et at., L}BS). Therefore, since the present investigation is a preliminary exploration of. trenils in a series of structures, it seemedadequateto choosethe simplestvariant of the extended Hiickel methodwith fixed VOIP and exponents. Finally, it is important to note that one of the biggest deficiencies of the extended Htickel methodis its failure to take adequate account of the Coulornb,interactions. The method works the best for moleculeswhere the electronegativity difference,Ax, between bondedatoms is small. However,it starts to break down when Ax is greaterthan approximately1.3, the breakdownbeing completewhen L1a 2 2.5 (Allen, 1970).Thus, when heteropolar substances with intermediatebond type (like the Si-O bond in a silicate whereAx = 1.2) are studied, EHMO theory may be used to qualitatively diagnosethe covalentaspects of the bonding.Accordingly,it is of particular interest to apply the EHMO method to silicate structureswhich have been found to conform remarkably well in the past with Pauling's rulesl for ionic crystals yet which also conform in many instanceswith a modelthat includescovalentbonding. Tnp Rnr,erroNsurpBprwnuN Si-O (br) BoNo Ovpm,epPopur,errox ANDrHE O-Si-O aNo Si-O-Si ANcr,ps In a study of severalorthosilicates, Louisnathanand Gibbs (1g72a) have found that the tetrahedralvalenceanglesin hypothetically distorted SiOetetrahedrahave a pronounced effecton n(Si-O), the wider O-Si-O anglesbeing associated with bonds of larger overlap populations. They also showed for a number of silicates (1g72b) that a correlation can be made betweenthe mean of three O-Si-O angles, (O-Si-O)3, and the length of the Si-O bond commor to these three angles,shorter bonds tending to be associated with larger values of (O-Si-O)a.McDonald and Cruickshank (l967a) and more recenily Brown and Gibbs (1970) have also shownthat shorber Si-O distances are typically involved in wider O-Si-O angles. Although Baur (1g20) has also indicated that shorter Si-O distancestend to be involved in wider O-Si-O angles,his geometricalmodel of a Si atom rattling
lAccording to Bent (1968) Pauline's mles ma5.r have a more universal application as structural principles than heretofore realized because when suitably rationalized they may apply to covalent as well as ionic compounds, perhaps even to metallic compounds.

1588

BARTELL, AND YOVT GIBBS,HAMIL, LOAISNATHAN,

is not realizedin general within a rigid"tetrahedronof oxygenspheres . in the silicates (Louisnathanand Gibbs, L972b) (L'iebau, and in siloxanes 1961) The Si-O-Si angles in silicates anglesas although (Noll, 1956) are usually between130o and 140o, in Si2Oz of 93" Except for a,nangle wide as 18Oo are not,uncornmon. bonding A are rare. (Anderson lessthan 120" and Ogden,1969),angles the predicts that model that includes Si (3d) orbital participation beangle as the Si-O-Si length of the Si-O(br) bond shouldincrease narrower (Cruickshank,1961).Moreover,as the Si-O-Si angle comes betweenthe si-atoms and repulsions narrows,increasingelectrostatic o-bond s-characterin the O(br)-orbitals (i.e.,a decreasing decreasing strength) are additional factors that are predicted to lengthen Si1961;Brown et a1.,1969)O(br) (Cruickshank, fn a re-investigation of the crystal structure of zunyite, Louisnathan and Gibbs (1972c)have found that the sizeof the tetrahedral angleshas a pronouncedeffect on zr[Si-O(br)] in Si,Ou- ions with linear Si-O-Si linkages.Thus, if {to(br)-Si-O(nbr)l > {[O(nbr)-Si-O(nbr)], then nlsi-O(br)l {[O(nbr)-Si-O(nbr)], then n'[Si-O(br)] = n'[Si-O(nbr)] whereas if { tO(br)-Si-O(nbr)l n[Si-O(nbr)] (seeFig. 2). These results calculated with all Si-O bond Iengths clamped at 1.634 imply that the magnitude of the tetrahedral angles plays an important role in establishing n'[Si-O(br)] in the the nature of the relationship Si-O(br)-Si linkage. In order to assess between the Si-Oftr) bond length and Si-O-Si angle, we calculated ions n[Si-O(br)] as a function of Si-O-Si angle for the three Si,O"z6shown in Figure 2. The results calculated with Si-O : 1.63A and a Si(sp) valence basis set are presentedin Figure 3a. Regardlessof the size of the tetrahedral angles,n'[Si-O(br)] increasesnon-linearly wil}r increasingSi-O-Si angle,the largestoverlap population being associated with the 1800 angle. Analyses of the linear coefficient, c6;, and the overlap, 8o;, matrices indicate that the changein z[Si-O(br)] is related to concomitant changesin both the o- and zr-bonding potentials. In both the o- and other words, widening of the Si-O-Si angle increases r-bond. strengths as proposed by Cruickshank (1961), Brown et q,I. (1969), and Brown and Gibbs (1970). Using results provided by the theory of atomic orbital hybridization, Louisnathan and Gibbs (1972c) have proposedthat the Si-O(br) bond length should vary as a function of -l/cos (Si-O-Si). When the n'[Si-O(br)]are replotted as a function of -l/cos (Si-O-S;), a well-defined linear relation (Fig. a) is realized. The trends predictedby EHMO theory are similar whetheror not the Si (3d) orbitals are includedin the calculation (Figs. 3a and 3b),

MO CALCALATIONS FOR SILICATE IONS

1589

(o)

(b)

(c)

Frc. 2. A comparison of Si-O bond overlap populations (the decimal fractions listed adjacent to the Si-O(br) and Si-O(nbr) bonds) calculated for three Si:Oz6-ions (Da,, point symmetry with Ca along the Si-O-Si linkage) where (o) {[O(br)-Si-O (nbr)l > dlo(nbr)-Si-O(nbr)1, (b) *[O(br)-Si-O(nbr)] : d[O(nbr)-Si-O(nbr)] and (c) {[O(br)-Si-O(nbr)] < {lO(nbr)-Si-O(nbr)1. The calculation was made using a Si(sp) valence basis and with all Si-O : 1.63,i. Note that z[Si-O(br)] > n[Si-O(nbr)] for the conformation in (o), nlsi-O(br)l - z[Si-O(nbr)] for (b) and that n[Si-O(br)] < z[Si-O(nbr)] in (c). (See Louisnathan and Gibbs, 1972c). suggesting that the observed steric details of a tetrahedral ion in a

silicatemay not be usedto establish the involvementof the 3d-orbitals in the formation of the Si-O bond.This is in agreement with Mitchell's (1969) assertion that "one cannot, to establish . . . expectexperiments whether d-orbitals are (really' used anymore than experiments can show s and p orbitals definitely occur in bonding of the first row elements"(seealsoBartell et aI., l97A). Si-O Bono LrNcrn Venrerrolv rN Low-QuARrz, I"ow-cnrsrosAr,rrn,ANDCopsrrp The silica polymorphsare possiblythe most appropriatestructures for examiningthe dependence of Si-O (br) bond length on both the O-Si-O and Si-O-Si angles,because(1) there are no bonds other than Si-O(br), (2) all oxygensare two-coordinatedand bridge two tetrahedra,and (3) A((O) : 0. For our analysis,we have chosen data from three preciselyrefined structures,all with e.s.d.'s less or equal to 0.0064: low-quartz (Zachariasen and Plettinger,1965),low-cristobalite (Dollase,1965),and coesite(Araki andZolLai,1969)(GroupA

GIBBS, HAMIL, LOU ISNATHAN, BARTELL; AND YOW

(o)
o7a

(b)

o50

o
I

o48

./

oo?4 o
@

of? o46

.t'

t40

ts

si-o-si(.)

si-o-si(.1

Fro. 3. Si-O(br) bond overlap populations calculated as a function of the Si-O-Si angle for the three pyrosilicate ions depicted in Figure 2. (a) Si(sp) basis with atl Si-O = 1.63A and (b) Si(spd) basis with all Si-O - 1.63A. Si-O(nbr) bond overlap populations for each ion increase only slightly with Si-O-Si and accordingly are not shown.

in Table 2). The data for keatite and low-tridymite werenot included in the analysis for reasonsgiven in the next section.The three structures chosen provide twelve individual Si-O(br) bond lengthsvarying from 1.598 to 1.631A. Figure 5c is a scatterdiagram of Si-O(br) bond length versus (O-S,i-O)3 angle; tr'igure 5b shows Si-O(br) versus [-|/cos(Si-O-Si)]. Using the estimatedstandarderror of the slopes for the lines fitted to the distributionsin Figures5c and 5b (seeTable 3), the null hypothesiscan be testedthat the true slopein each case is zero; that is, that the Si-O(br) bond length is independentof (O-Si-O)3 or -1/cos(Si-O-Si). Student's ltl calculates tn be 3.3 and 2.3 for the data in Figures5c and 5b respectively(Table 3). Since these values exceedthe 9O percent confidence level (c/. Draper and Smith, 1966)of t(10,0.90) - 1.4,we can rejectthe hypothesis LhaLa relationship between Si-O(br) and -1/cos(Si-O-Si) or (O-Si-O)3 might not exist. We have usedthe function [-l/cos (Si-O-Si)] rather than the angle itself becausez[Si-O(br)] vary non-linearly with the angle but

MO CALCULATIONSFON ilLICATE

IONS

1501

(o)
o.50
F

I o.cs o
I '= ir O.48 c

o.47
t30 t40 r50 160

r70

t80

si-o-si (.)

(b)
o.50
I

0.49

I '=

;J c

O.48

o.47
t.6 t.5 t.4 t.3 t.2 t.l l.o

-llcos(Si-O-Si)
Frc.4. Plots of ztSi-O(br)l as a function of (a) Si-G-Si angle and (b) -1/cos(Si-O-Si) where the bond overlap population was calculated for the conformation in Figure 2b and a Si(sp) basis set.

7592

GIBBS, EAMIL, LOUISNATHAN, BARTELL, AND YOW

linearly with [-1/cos(Si-O-Si)] (Fig. a). However, even if the relationshipbetweenSi-O (br) bond length and Si-O-Si angle is ascan again be sumedto be linear, the hypothesis of no interdependence rejected at the 90 percent confidence level (seeTable 3). When the obSi-O(br) lengthsare estimatedusing the interceptand coefficients tained from a multiple linear regression analysis,using both (O-Si-O)3 corand [-1/cbs(Si-O-Si)] as independent variables,a reasonable respondence beiween the experimental and estimated distancesis observed(Fig. 5c and Table 2). Finally, two commentson Figures 5o and 5b are worth making: (1) the quantity [-1/cos(Si-O-Si)] the former may be a better definedvariable ihan (O-Si-O[ because includesa more accurateaccountof the hybridization characteristics of on O(br) than the latter doesof the hybridization characteristics slope [-0.05(2)] for Figure 5b is statisSi, and (2) the calculated tically identical with that [-0.0E4(1)] obtained for n"[Si-O(br)] deversus [-l/cos(Si-O-Si)] (Fig. ab), an interestingcoincidence

Table

2 tran .ooldldtlon and Etldtne' to! slllc' truober' <d>'

Sr-o(bt)

bond ad

rengths, A!(O) Si-o(b!)

s14(br)-sr to. 3111c6

angles, PolrrPhs, w.

orygen

sUleates Sl{(br)-St 0 and

Group

Ar

bond PolForPhe

dt.tsnce qhere

a((o)io

data sngte <cN>'z 0

s1-0(b!) sl-o(r) sr-o(2) sr(1)4(r) sr(2){(2) s1(r)-0(3) s1(2){(3) sr(r){(A) sr(2)-o(4) sI(r)4(5) 51(2)-0(5) sr-o(l) sr-o(l)' 1.601 r.608 r.600 r.6oa I:607 r.619 r.598 r.625 1.63r 1,511 1.603 1.616
1 6045 1.600 l. @8 I 611 l.6115 I 5240

s1-GSt

;;;Gi

<cN>

a<(o) Dorrade (1965)

146,8 $00 145.E 145-0 150.4 1!6. r

t.r95l r @00 L 2392 r,2204 1.1501 1.3874

20

0.0

2.O 20 20 2.0 20 2.O

00 OO 00 0.0 00 0 0

Arakl and zoltar (1969)

I 6095

r41.5

I 246C

Zacbrkden t?lettlnger (1965)

Cloup

Dr

S1{(br)

bond

dl.tdc.

v!.

Sl{(bt)-Sl

.41.

d.t.

for

.Ulc.t..

ad

.tlosE6 l-527

vh.r.

ar(o)-0.0 rto 3

tor

au

oqgu 2.8 2.1 2.9 0.0 00 0 0 &|'oald a crulck.Mnk(1967b)

s14(4) s1-o(l) s1-o(t)l sr4(r) s1{r(2) sr-or(r) sr-0r(2) s14I(l)

H3S1-O-SIB3 (q3)6(sro)3 (cB3)E(sro)4 (cH3)ro(sio)5 (cff3)r2(sio)6 lbzs12o7 Er2Sr207

L.627

l.l5l2

l:3i3
r.6052

r.6re
1.6052

r32.e
UO.0

r.4690 LO r,0194 I 01t7 l.2t4t r.s62 1.223E r.2034 l.1594 l0 l0

rr.ch.r(1969) Prdtt (P.r.oul cd.)

l:?31 i:S
1,6s. 1.63t L.622 L 620 r,622

r.5e4s r6s.6 r 5e4r

I 634 1.63t L.522 I 620 t.622 1.626 r 632

Gtbb., E!cc& .od (196!) e.sh.! 2.7 2.0 2.0 2-o 2.o zo 2.9 29 00 0.0 00 o.o o.o o'o 0.0 0.0 srolh r shepel.v (1970) rl4Dlg@ 4.r!., (1963)

r5e.!
1a{.1 13r.6 144,0 t46.2 149.6 1E0.0 180.0

ob.r@t(1e72)

sr4(1) sr{(r)

1.626 I 6t2

MO CALCULATIONS FOR SILICATE IONS

Tab]e Group Cr s1-o(br) bond dlrtance v. 2 (cont.) s1{(br)-S1 aqle data tor elltcare!

1593

aher o(br) 8"3s14&5o25 sr-O(r) 1,599 r.599

1.

ruo coordl@ted l.mOO t 7 -.lO sbmoo 6!d et. (1970)

t6O,O

Lw rbrte

3ll[3i:3:[:]

t:8li
r.603 1.620 i.3li 1.614 i:331

r.610

16r.2

1.0564

2.s

-'04

Ese re'4"

(re6e)

:ii[:]-8S[:]
LN Cordlerrce tudd& cordlerltG :l[i]*[:] Danburlrc KlsuaroPlrte :1[l]1[1] si{(l) st(3)-o(6) sr(4)_o(6)

i'.211 r.6185 B'.7

L.3et2 2.s ::3X

.02 .o2 ctbb. (t965) hsher (1e67) (f97r)

r.5o5s 1.614 1.644

Lts 5 r36.E r3r.e

r @oo t.37l8 L.4st4

2.7 X.7 1.4

oz -.25 -:33

phrulp. !.!.f!., ** !!'q!"

(re67)

*"lll#,,."

3il[;]:3:3i :i?[:i:333] 3i[i]:3[i]

i:133 i:3i3 i.z:rt i:33i

1.66 r.629 1.633 1,621 I.613

r.63r r'6125 r'534 r.617r

r.06 r.oz9 1.613 1.521 1.513

rs'8 r55'e r4o.r r5r.5

143.E 143.0 8t,O 141.1 ta2.2

r.5304 r'@$ 1.303s r.r37e

L,2392 L,z52L r.3250 r.2850 L.2622

2.s ::ff "* 2.e -'.31

6d !r''v (re64)

(lnort EPidrdFlt :1[li:3[1i

s1(r)-o(r) s1(2)_o(6) slG){(E) krltullr. c'l61Eat6rt. s1(r){(7) s1(r){(7)

(reIr) 2.1 -'os hutid z.E ::3i 'o**

.O .07 ,Ol 3.2 3.0 -.13 _.03 H&bU !!.q!,, (r9tr)

'rd !'4 (re7o)

:l[i]][;i
ctun.rltc s1(I){(7)

i:!ii
1.613

t.5z6s r3e.7
1.613 r44.!

r.3rr2
L.223E 3.0

-:33
-.@

:|[]li[;i
1r@llr. Gbucopbo. c-c6te!.d sr(I){(7) Sr(1){(7) hs1(r){(7)

i:lli
1.616 1,6t1 I 616

r.5re
r.616 l.6rt I 616

142.4
r39.! L17.2 lat.O

1.2622
r.3l9o t.IA97 r.2m 3.2 3.2 j.O

-:31
;.8 -.tl -.03

rr{.r

(1969)

r.ptb

!!.!1.,

(1969)

c@ltrst@lt' c@ln8toa1t.
b-

:l[i18]
Sl(r){(7)

i..232
1.626

r.628
t,52A

r&.0
t39.I

r.ss
1.32S 3.0

-:3;
-.03

?rtdtlve

:l$lil[;]
51(r)s(7)

i:31
t.@3

t.622
1.603

r3e.8
l4l.O

r.sez
t.a$

-:83
-.03

:i[]1i8]
protryhlbot. s1(r){(7)

i.fll
1.524

r.6345
t.624

136.r
137.1

r.3373
1.3651 3.1

-:B:

:l$11[ii
hthophylllte si(I){(7)

i.!ll
1,fl5

r.62r
r.6$

140.6 r.2$r
l4l.a L.27% 3,2

-:Bl
-.07

-.Ot

cibbr

(1969)

sr(t){t(7)

3i$ifl[:]
:i[ili[3]

1.6t7

i:fli

r.6,6
r.617

140.6
t3r.g

r.2e6
1,3a99

-.31 r l q . r
-.Il

(t970)

i:|?i

r.6275

r&.3

i.orar

3.5

-'03 brb'c (re6)

,",.-""" :::.. ,::,, ;fi :.,.:,,.::,-.;.::: il;i;fi

spite the fact that all n(Si-O) were calculated assumingall Si-O equal 1.634 and all O-Si-O angles: 109.47"in Figure 4. Tnu Connpr,erroN Bnrwnnu Si-O (br) BoNo LnNcmr eNo Si-O-Si Axcr,p rN Srnucrunns WHpnn a((O) rs ZERo In structures of low-quartz, low-cristobalite, coesite,hemimorphite, thortveitite, beryl, emerald, benitoite, YbsSizO,T, Er2SisO7,and five siloxanes,all the oxygen atoms receive the same bond strengttr, i.e.

1594

GIBB!, HAMIL, LOAISNATHAN, BARTELL, AND YOW

(o)
r64 r64

(c)
a a -

=
!
6

'ez

o
ooo to
I

162

a' a 1I o

U'

t.

r60

at

t60

r50

t60

(o-si-o)t

si-o-si(")

(b)
r64 r64

(d)
a.
a

!
o

,ez

3 t62
o
I (,) t60

lo a oo
t60

a
| 60 t4 | 62 1.64

r5

t2

to

si- o(.st.l(l)

-llcos(Si-O-Sil

bond length data from Table 2, group Frc. 5. Scatter diagrams of si-o6r) A, plotted as a function of (a) Si-O-Si, (b)-1lcos(Si-O-Si)' (c) (O-Si-O)s: the average of the three o-si-o angles involving a common si-o bond and (d) si-o(est.)A using the results of a multiple linear regression analysis with -1rlcos(Si-O-Si) and (O-Si-O)" as independent variables'

((o) = 2.0 and a((o) = 0.0.The si-o(br) bond lengthsand si-o-si anglesin thesestructuresare listed in Table 2 (GroupsA and B)' The scatter diagram of Si-O(br) versus Si-O-Si angle and [-l/cos(SiO-Si) ] are given in Figures 6o and 6b, respectively.For lhe 27 that individual si-o(br) bond lengthsin this data set, the hypothesis (2) of and arrgle Si-O-Si (l) versus Si-O(br) the true slopes of The calcuwas t'ested. zero are Si-O(br) versus [-l/cos(Si-O-Si)] and Itl- values partial correlationcoefficients, slopes, lated intercepts, 2-5 and 3.6 for ate values are given in Table 3. The calculatedltlthe critical exceed these Because Figures6o and 6b, respectively. lfls that null hypothesis the 1.3, we can reject value of ,(25,0.90) not be correlated might Si-O (br) bond length and Si-O-Si angle t (25,0.90)) . This resultis contraryto Baur's (actually 2.5 alsoexceeds Si-O (br) (1971)conclusion that a correlationcannotbe madebetween : his conreached 0. He and Si-O-Si anglefor silicateswherea((O) clusion using data from keatite, high-tridymite, low-quartz, low-

MO CALCULATIONS FOR SILICATE IONS

1595

The correlations presentedin our Figures 6a and 6b are somewhat improved (seeTable 3) when the data from ybrSizOT,Er2Si2O7, and
Table 3 Ln[ercepts, a^r slopes, brr and correlation coefficieDts, r, for.]-inear regresslon eqdatlons fittad ro dara in TabLe 2 and Flgs, 5-7. ltls calc. for Ho:Bl = O; all ltl's exceed a two-slded 902 1evel test Group A of Table

2
t

bt
S1-0(br) bond length vs. S1-O-S1 angle for slllca polynorph data (Fig, 58) Sl-O(br) bond length v6. -1lcos(Si-0-S1) for sllIca pollnorph data (Flg. 5b) Si-O bond Lengtha vB, <O-Si-o>a for s1l1ca polynorpH dats (Ftg. 5c) S1-0 bond length ve. SL-o(est) for sLllca pollnorph data (F+g. 5d) L,677

Itl 1.8

sanple size

-0. ooo4 (2)I

-0 .48

1.539

0 . 0 6( 2 )

0.57

2.3

4,094

- 0 . 0 2 3( 6 )

-n

77

-0.168

1 . 1( 3 )

0.76

3.7

Groups A and 82 of Table S1-0(br) bond length vs. Sl-o-St angle; Flg. 6a S1-0(br) bond length v. -Ucos(sl-O-Si) ; Flg. 6b
rL. tq) I. O6J

-0.0009(2) -o,oo04(2) (1) 0.08 (2) 0.06

-o,72 -0,4s 0.7s 0.58

4.8 2.s 5.3 3,6

24t 27' 24't 27'

{ 1. .5 54 15 6 '1

Groups A, B, and C2 of Table 2 Si-O(br) bond length vs, S1-0-Sl angle; Fig, 7a Si-O(br) bond length ve. -1lcos(Si-o-Sl); Fle. 7b 1 1.,5 78 04 0I8 '1 1 1..5 56 51 4 '1

-0.0005(1) -0 ,0004 ( 1) (9) 0. 0 s 3 0,04( 79 )

-0,51 -0.44 0.53 o.49

5.1 4.3 5.5 5.0

78r 81', 78r 81'

re,s.d,rs

are glven 1o parentheses and refer

to the last

digit.

2The data fron thortveitite, Errsiroil glven in the flrst atatlstlcs iow'of

and ybaslroT rrere not uaed to obtaln the thc dati sEtb enclosed by braces (see text).

1596

HAMII" LOU-I&NATHAN' BARTELL, AND YOW GIBBST

(o)
t.66
'a

t64
a\o
.cl

r.62

o
I

--.1
taa\-

t '
--

o o

t-a-

r.60

\.-= . O _ _l
a

r.58

r30

t40

r50

160

170

r80

si-o-si(")

(b)
r.66 r.54
-o
L

\-o -o

--o -\ a

.o \. ao
-O\ !r' oa o-'-r -O

o
I

1.62

t.60

'

- - -t \f.,. a

t.58 1.6 1.5 t.4 1,3 t.2 l.l to

-llcos(Si-O-Si)

Frc. 6. Scatter diagrams of Si-O(br) bond'length data from Table 2; groups A and B, plotted as a function of (a) Si-O-Si angle and (b) -1lcos(Si-O-Si)' The dashed line in (b) is a least aquaxesline. The dashed line in (a) is transgenerated from (b). The open circle plots are data for thortveitite, Ybosiroz and ErgSLOn.

MO CALCALATIONS FON SILIAATE I.ONy

I8S7

thorbveititeare excluded(open'symbols in Figs.,6aa,nd.'6b). In-these

Rm,errvp ConrnrsurroNs ol. -1/cos(Si-O-Si), a((O) exn (Cff) To rHE Venr,lnrr,rryoF TrrESi-O (br) BomuLnxcru As' a((O) and the. mean coordination number, (CN), of oxygen bonded to silicon have also been suggested as determining factors of the Si-O(br) bond length (Baur, lg7l), an examination oieach in the

The results are listed in Table 4 in the order ranked by the stepwise
Table 4

Analysls of varlance: Multiple the data used to prepare Fig. the dependenr variabte; t(74, iodependent variable was found

linear regression analysls for 7 wlth Si_O1try bond length as = O.9O) 1,7, The order of the by scepvise reglessioD oethocls,l

fndependeot -1lcos

Varlable

ltl

Partial

Addeal Regres6ion Su of Squares

Sdple

Slze

(Si-O:Sl)

t' 1 6 '. o 4 t4'2

0'63 0;59

0,0043 0.0038

81',

AE (o)

o.44 0.41
U.J)

0,0020 q..0020 0.0005 0.0006

78r 81, 78, 81'

<cN>

F,2

0,34

llhe

data stat.lsties

from thortveitite, ErrSi,Oa, glven ln the flrst iow'of

and yb^Si"o, the datf s6tC

were not e.rclosed

uaed to obtaln by braces_ (see

the text).

1598

BARTELL, AND YO'W GIBBS,IIAMIL, LOAISNATHAN,

method (c/. Draper and Smith, 1966).The ltl- valuesinregression dicate that all three variables contribute significantly to the varia-

that the data are omitted for structures a random sample in the sense where A((O) is relatively large and where O(br) is coordinatedby more than two atoms. Therefore the regressioncoefficientcalculated data set.Howevet, for our data probablywill not apply to an expanded number of o(br) are moderately sinceA((o) and actual coordination correlated,we cannot,concludea priori whether the magnitude of the slope associatedwith (cN) will be larger or smaller than 0.006 or whether (cN) witl make a significant contribution to the regression of a((O). in the presence sum of squares (br) versus Si-O-Si angle for a wide length bond Plots of Si-O Brown and Gibbs, 1970) (Cannillo a1.,1968; et variety of silicates (see Table 3) irrespective or 7b 7,a as Figures exhibit the sametrend Accordingly, it oxygen' bridging the of of the coordination number in part to the (br) related is bond si-o appearsthat the length of the (CN), with the or a((O) of value of the $i-O-Si angle regardless result this Although angles. wider shorter bonds being involved in the (3d) parorbital si includes that with a covalentmodel is consistent orbitals that these earlier ticipation, one cannot concludeas indicated are definitely used in the compositionof the si-o bond (Bartell et al., 1970). Si-O THEOssunvED BntwnnN n(Si-O) AND Tnn Rnr,erroNSHIP BoNp LnNcrn As both O-Si-O and Si-O-Si angles appear to exert a pronounced rz(si-o), we calculatedthe bond overlap popularole in establishing tions for isolated and polymerized tetrahedral ions in ten silicates (Table 5) using the observedO-Si-O and Si-O-Si anglesand clamping all si-o at 1.63a.The calculationfor a valencebasis set consisting of silicon 3s and 3p and oxygen2s and 2p atomic orbitals yields bond overlap populations which, when plotted against the observedsi-o distances(Fig.8), show an apparentlinear relation with longerbond with smaller overlap populations.As expected, lengthsbeing assoeiated

(o)
t.66 a o t.64

3 r.ez o
I

o o

an t.60

o foo ao a

. a

. a
a

o I

r.58

r30

r50

160

r70

r80

si-o-si(")
r.66

(b)

t.64

ll

1.62
I

o
6
r.60

t
a

r58
t6

r5

t4

t3

1.2

tl

t.o

-llcos(Si-O-Si) Fra. 7. Scatter diagrams of Si-O(br) boad length data from Table 2, groups A, B and C, plotted as a function of (a) Si-O-.Si angle and (b) -1lcos(Si-O-Si)The dashed line in (b) is a least squares line. The dashed line in (a) is transgenerated from (b). The open circles are data for thortveitite, Yb"StOr and Er"SLO". The reported e.s.d.'s of ihe Si-O bond lengths for the structures given in Table 2 are all less or equal to 0O1A.

1600

GIBBS, HAMIL, LOUISNATHAN, BARTELL, AND YOW

Table 5

an

b..t.

.!d

b..!t

b!'
r1-0(l) sr{(r), si4(2) sa-0(3) st-0(t) si-o(2) sr-o(4t mortv.lrtr. sl-o(l) st-0(2) sr-0(t) sl-0(4) sr_0(t) st_0(6) ar_0(7) Sl-O(r) st-o(l)l 8r-0(2) sr-o(I) sr-0(I)l st-0(2) 3r-0(r) sr-o(3) sr{(l} s!-o(r)l 8r{(2} sr(r){(r) st(r)-o(2) sr(r)-0(3) sr(r)-0(a) sr(2)-0(4) sr(2)-0(5) s1(2){(6) s1(2){(7) sr(3)-0(r) 51(l)-0(6) st(3)-o(9) st(t)-0(3)
C.st0l

!.!:!,(lrl
1.66 l.t4t 1.517 1,500 |,626 1,63r

lLeLit o.(8! o.as 0.t06 0,511

t ="* 0,4t5 "=","t O,rLl 0.478 0,155 0 942 0.515 0,946 0.530 0.5@ 0.505 0.495

t* 0.734 0,739 0,955 0,97E

o,922 0,93! o.?56

.4!s h!ll, c!!b. .nd ilbba (r97r)

C!!rct.h.d

(1967)

Le21 t.60t

t,627 l a28

0.494 0.501 0.!03 o.{91 o,a6E 0,510 0,50E 0.505 0,50E 0.50! 0.505 0.50t 0.t0! 0,56 o;til 0.4s 0.4t6 o.!or 0.50! 0.509 0,464 0 4!6 0,115 0.52r 0.506 0,411 0.48! 0.512 0,501 o.att

0.506 0.t0I 0.502 o.(i2 0.405 0.515 0.t2t 0.5rr 0.t30 0.503 0.t22 0.51t 0,t0{ 0,t16 0.t06 0.499 o.a?l 0.521 0:531 0 514 0.4t0 0,165 0.41! 0.545 0.523 0.454 0.462 0.t23 0.t16 0 4(5 0.521 0 52! o.462 0.488 0.549 o 522 0 469 0.461 o 525 o 555 0.45! 0.521 0.499 0.451 0.515 o.a6E

0.?61 0.9?t 0.926 o ?5E 0,7t1 0,941 0,944 0,tt8 0 742 0,9!9 0,rr7 0,182 0 9t9 0 1A2 0,162 o,?75 0.7tt 0,9{o 0,941 0.940 o,ttt 0.761 O 1Lt 0,959 0.934 0.741 0.t45 0.9{t 0.919 0.751

0.115 0,925 o.926 0,161 o,752 0.960 0,96! 0.7E2 0,8r5 0,912 0, t95 0 800 0.78t 0,7aE 0,162 o tx' 0 9n{ 0.98t o 142 0,7t0 0. trt 0.999 0 960 0 7l! o,t2t 0.960 0.98t 0 69! 0,96! o 964 0 703 0.17L 0.693 1 00r 0 959 0. t18 0,724 0 97r LOl6 0 tor b 950 0.918 0.t02 0.951 0 723 rrol.r (1969) Ttpp. .Ed fldllton (19?1)

tosilltn.

1.623 l.a2E

1.616 r,st

hrrld

l.6s l.t8t 1,621 l.!94 t.59t 1.620 r.603 1.6t6 r.6x 1.646 1.60t 1.507 l.a2l I 6t6 L,612 t.6t9 1.596 I 606 1.460 1.678 1.517 r.595 1.698 l.6ot 1.603 1.503 1.626 1.701 1.589 t.609 L65t 1,669 t.600 I t5l 1 561 1,504 L6lr t.649 t.6tl L,641

h8h.!

(1968)

l.ryl

b.ib.r

(1968)

rld acbrt...r (1965) Pl.rcrnr.r lt.ch.r (!969)

lr.d

.!d

rx.o!

(rt69)

sr (r)-0(l) sI(r)-0(2) sr(!)-o(3) s1(l)-0(9) sr(2)-0(r) s!(2)-o(.) sr(2)-0(5) sr(2)-0(a) s!(3)-o(5) sr(r)-0(7) s!(3)-0(6) sro)-o(9) sr(2)-0(2) sr(2)-0(3) sr(2)'0(8) sr(3)-0(6) sr(3)-0(3)

Donily rtrd Allqn (1968)

Fo.rt.!tr.

sr-O(t) sr-o(2) sr-0(3) sr-o(l) st-0(2) s1-0(!) sr-o(4)

1,614 1 654 r.615 r t70 r 648 r,551 1.661

0 515 0,400 0,469 0.506 0.{93 0,492 0,487

0.525 0,4t0 0 487 0.545 0 484 0 4!2 0,{69

0 935 0 878 0.898 0,918 0.900 0.899 0.890

0.952 0.862 o a90 o 98t o 65 0sl 0.861

8106.d Cllb. (1972); but.n.rh.n .nd c1bb. (r972.) Fort, Phlutp. .nd Orb6. (rn Dr.pr..!ron)

D.tolrr.

the overlap populationsobtained using observedtetrahedral angles and bond distances in the calculationsshow a similar but better developedtrend when plotted againstthe observed bond length (Fig. 9). Theslopes,intercepts, corelation,coeffi cients,and It |- statisticscalculated:for the data in"Figures8 and g are given in Table 6 and Show that both trendsare highly significant. The curvesof Bartel"let at. (1970)which relate bond length to bond overlap population are similar to those obtained.,inFigures 8 and 9

t70
W I T H O U Td O R B I T A L S ; o Si-O = 1.53A tr: A D V O o c ,O Morgorosonile Beniloile Bcryl Emerold Quorlz Tourmoline 0ioplose Thorfveilile + Forslerile x Dololile

r.69

r68

t67

r66

r65

164

E r,63 I o
-lU' | 62

t6l

r60

>o
159
T

r58 r57 r56 r55

o47

048

049

o50

051

o 52

0.55

n( s i - o )
Fro. 8. Scatter diagram of Si-O bond length data plotied against; z(Si---O), calculated using observed valence angles, assuming'Si-O = !63 A; aud excludilg Si(3d) orbitals for the minerals Iisted in the upper right. Si-O(br) bonds aie iq dicated by open symbols and Si-O(nbr) bonds by bolid ones.'Data takbn from Table 5.

GIBBS, HAMIL, LOAISNATHAN, BARTELL, AND YOW

l?o

wrTHOUt d OREIIALSi
t69

) Si-O (obe

t6t

r57

O Nigh 9r.nur.

CaSiOr

t66

t65

-" ..\

d\,

164 o o

o o

r6s

"o
t62

o\.'
l5l OeO t60 DD r59 \ '

r56

r5c

n(Si-Ol

Frc. 9. Scatter diagram of Si-O bond length data plotted against n(Si-O)' ealculated using the observed distances and angles and excluding Si(3d) orbita.ls for the minerals listed in the upper right of this figure and Figure 8. Si-O(br) bonds are indicated by open symbots and Si-O(nbr) bonds by solid ones. Data taken.from Table 5.

suggestingthat the overlap populations calculated for the sulfates' when the 3d basisfuncphosphates, and the silicatesare comparable tions are neglected.Correlations can also be made betweenthe Si-O bond lenglh, the net non-bonded geminal populations (c/. Barbell on Si and O; however, et o,1., 1970), and the net chargedifierences inasmuch as the non-tetrahedral cations were not included in the calculations,such correlations are not appropriate here. to include When the valenceorbital basis set of silicon is extended the five Si(3d) orbitals, the EHMO calculation gives n,(Si-O) that again correlate with observedSi-O bond lengths but as two separate trendswith the overlappopulationsfor the Si-O(nbr) bondsexceeding those for the Si-O(br) bonds by about 20 percent (Figs. 10 and 11, Table 5). The overlap populations calculated using the observed

MO CALCULATIONS FOR SILICATE IONS

1603

tetrahedralanglesand all Si-O = 1.63Aare plotted againstSi-O(obs) in Figure 10 whereasthose calculatedusing observeddistancesand anglesare plotted againstSi-O(obs) in Figure 11.Thetrends in both scatter diagramsare highly significantas evincedby the ltl -values (Table 6). The correlationsare much better developed in Figure 11 wherez(Si-O) were calculatedusing the observed and Si-O distances angles. In addition,the slopescalculated for the Si-O (br) bond trends (Figs. 10 and 11) are steeper than thoseof the Si-O(nbr) bonds.The Si-O(br) bond trends for the data given in Figures8 and 9 alsoappear to be steeper, indicating that the Si-O(br) and Si-O(nbr) bond overlap populationscharacteristicallyconstitutetwo distinct populations evenwhen a Si (qp) valencebasisset is used (Table 4). The difference calculatedin n.(Si-O) for the Si-O(br) and Si-O(nbr) bondsis due in
Table 6

Intercepts, regresslon

a^, slopes, bil e{uatlons fitted

and correlation coefficients, ro dara ln Flgs. 8-11; ltl

r, for tt

linear = o o:Bl for

o
observed S1-0 bond length vs. n(Si-O) calc. f,or Si-0 = 1,63fr; F1g. 8 Observed S1-0 bond length vs. glsl-0(br)1 calc. for Si-O = 1.63; Flg. 8 Observed Sl-O bond length vs. nlsi-o(nbr)l calc, for S1-0 = 1,63 ; I'tg. 8 Observed S1-0 bond length vs. n(Si-o) calc. for obs. S1-0; Fig. 10 Observed S1-O bond length vs. ntSt-O(br)l ca1c, for Si-O = 1,63; Fig.8 observed S1-0 bond length vs. n[Sl-O(nbr)] calc. for S1-0 = 1,63; F1g.8 observed Si-o bond length vs. nIS1-0(br)] calc. for obs. si-O; F1g, Il observed Sl-0 bond length vs, nIS1-O(nbr)] eale, for obs. st-0; Fig. 11

bl

l.l
-0.84 9 ,I

2.763

-z.zdL

3,025

-t

9., t

-0,89

8.3

-L,tt6

-0.77

5.3

2.L39

-7.024

-0,94

20.0

3,220

-2 .O7 6

-0,77

6.0

-0.816

*0.70

5.5

2.3L9

-0. 906

-0.94

13.4

-0.548

-0,94

L0.2

1604
t72

GIBBS, HAMIL, LOAISNATHAN, BARTELL, AND YOW

r70

WITH d OREITALS; S i- 0 . | 6 l l

j! r64 o o
I t62

v, t60
r58

o o

r56

154

o74

076

078

080

082

084

0S

O8a

O90

092

094

096

098

n(si-o) Frc. 10. Scatter diagram of Si-O bond length data plotted against ??(Si-O), calculated using observed valence angles, assuming Si-O - 1.68,4. and including Si(3d) orbitals for minerals listed in upper right of Figure 8. Data taken from Table 5.

part to the very different environments imposedon these bonds by our modeling of the tetrahedral ion in each silicate as an isolated molecule. Accordingto Bartell et aL. (1970),part of the difference may also be steric and part may be due to electrostatic forcesnot reflected in the bond overlap populations. The a(Si-O) valuesusedto prcpareFigures8 and 10 werecalculated with the Si-O distances clampedat 1.68Abut with observed O-Si-O and Si-O-Si angles.Clamping all Si-O distances at l.68A may eliminate the bias inherent in using the observedpositional parameters, but it can introducebias because the bond lengthsare not allowedto respondto differences in the bond overlap populationsestimatedby Hiickel theory. Moreover, for many complexpolymerizedSiOa ions, the Si-O bond lengths cannot,always be clampedat 1.68A and still retain the observed anglesand the continuity of the polymerized unit at the sametime. In thesecases, it may be possibleto obtain a reasonableestimateof the ra(Si-O) by using the observed distances and anglesin the calculations. This is because well-developed correlations exist betweenn (Si-O) ealculatedfor Si-O = 1.68Aand those calcu-

fl"t"i

MO CAI,CULATIONS FON yLICATE

IONS
ht)
NF

1605

qE

sE
@

o=
OP

o
r

.E; -x
XQ

c
o

6f
ar

D o
al, J F-

8 Oaa B
o
oQ

.b9 tr 0A
YA

EE
>,r4

E8
EO 9l

+.

.od

HS

tO ts

'

d
a 6

.Eq
xd !E ;i6

3co

*Q. o/ a: b.-

o/o

o
I - t^ t s o 9a vF
f h v

oJ
0 0 o

0 0

P ct
Fd

'Ho :S
dai

uor,
h

! . i

o
o
.P

iEg_EEq_EiEi
(sqo) o - !s

o
H

1606

AND YO'W BAR,TELL, GIBBS, HAMIL, LOAISNATHAN,

Iated usingthe observed positionalparameters(Fig. 12) (seeCameron, 1971). Concr,usroNs (1970) Allen has implied that EHMO results may be useful in determininga relationshipbetween bond overlappopulationand bond length relations like that obtained for the hydrocarbons(c/. Schug, 1972) but this is Lhemost he believes that it can do. Our calculations such a relationship appearto have been successful in demonstrating and suggest that at least part of the Si-O bond length variations observedin the silicatescan be rationalizedin terms of a covalentbonding model. Our results also imply that the steric details of a silicate cannot be used f,o proue the participation of the Si (3d) orbitals in a Si-O bond formation because similar structural trends are predicted a when they are omitted and a valencebasisset is used.Nevertheless, covalent bonding model including d-orbital participation permits an understanding of the X-ray emission(Dodd and Glen, 1969;O'Nions spectra (Urch, and Smith, 1971;Collins et aI., L972) and fluorescence (Revesz, 1969, 1971;Collinset aL,,1972) and the bondpolarizabilities 1971). In addition, it gives a reasonablygood accountof the trends in Si-O bond length variations. Consequentlya covalent bonding model that includes Si (3d) orbital involvement should not be dismissedas chemicallyinsignificant.SinceEHMO theory fails to take effects, the seniorauthor and his stuexplicit accountof electrostatic dents are presentlyundertakingMO calculationsat the next level of which involve the inclusionof the two electronintegrals sophistication as emto self consistency and refi.nement of the linear coefficients bodied in the CNDOI2 approximationof Pople, Santry, and Segal (1965). These calculations do take ordinary Coulornb interactions the CNDO/2 into account. It will be of interest,therefore,to compare present well with those as as study results with those obtained in the obtained by the ab iruitio method. Finally, the ultimate goal of any bonding theory for the silicates is to provide some insight into the physical laws that govern atom physical properties and stabilities. Molecular orbital arrangements, by theory in its simplest form has been used with moderatesuccess spectra,bond the organicchemistto rationalizereactionmechanisms, for a large number of organicmolecules length variations,and shapes (Streitwieser, 1961). The trends obtained in our study suggestthat extendedHiickel molecularorbital theory, unlike the extendedelectrostatic valence rule, may be used to classify and order the bond length variations in the tetrahedralportion of a silicate when A((O)

o54

o52

o48

o46

o.48

050

052

o80
lf) (D

b
O1

I a

o78

o
! o J o

o76
a'

o74

U)
c

o72

070

o96

c
laa

o,94

.).-'

o92

o 88

0,90

0.92

0 94

096

098

rOO

n(Si-O66) e Frc. 12. Bond overlap populations, rr(Si-O), calculated with Si-O = 163 A us. ra(Si-O) calculated with observed distances, both with observed valence angles. (a) For Si-O(br) and Si-O(nbr) bonds without Si(3d) orbitals; correlation coefficientr - 0.94 (Data from Figs.8 and 10). (b) For Si-O(br) bonds with Si(3d) orbitals; r := 0.90 (Data from Fies.9 and 11). (c) For Si-O(nbr) bonds with Si(3d) orbitals; r '= 0.90 (Data from Figs.9 and 11).

1608

GIBBS,HAMIL, LOAISNATH.A.N, BARTELL, AND yOW

- 0. Moreover, similar calculationsby Urch (1971) have provided valuable insight into the L2,s X-ray fluorescence spectra recordedfor silica glass. As the rewards are great, earth scientists are urged to considerthe use of MO theory in their interpretation of spectra, physicalproperties, transformaand phase order-disorder mechanisms, tions of minerals.Even if applicationof the theory provesonly moderately successful,it should, for example, improve our ability to evaluate evidencebearing on the physical conditionsthat prevailed when a mineral or a mineral assemblage forrned.
AcxNowtgocupNts We are grateful to Drs. G. E. Brown, Jr., R. G, Burns, J. R. Tossell, and D. R. Waldbaum for reviewing the manuscript and making a number of helpful suggestions.Professors F. D. Bloss, D. W. J; Cruickshank, P. H. Ribbe, and J. C. Schug, and Dr. M. TV'.Phillips are thanked for very helpful discussions and for critically reading the manuscript. G.V.G. gratefully acknowledges the National Science Foundation for its generous support in the form of grants GU-3192, GA-L?D?, and GA-30864X, and Virginia Polytechnic Institute and State University for providing funds to defray the relatively large computer costs incurred in the study. M.M.E. and SJ.L. gratefully acknowledge the NSF departmental $art (GU-8192) support in the form of research associateships. Appor.rrrx Stepwise regression analysis is a systematic and objective procedure for recognizing those variables that contribute most significantly to the variation in the response,regardless of their actual entry points into the model. As a first step, a correlation matrix is computed and the va.riable most highly correlated with the response variable is used to compute a linear regression. The second variable to be entered into the regression is the one whose pa.rtial correlation with the response is the largest, i.e., the one that makes the greatest reduction in the error sum of squares. Next, the method examines the contribution the first variable would have made if the second one had been entered first and the first variable second. If the partial F' of the first variable is statistically significant at some preselected confidence level, the fust variable is retained; otherwise it is rejected. Assuming that both the first and second variables make a significant contribution, the method selects the next variable to be entered, i.e., the one that now has the largest partial correlation with the responsegiven that the first and second variables a,re in the regression. A regression equation is calculated with all three variables and the third variable is tpsted for significance. Moreover, partial F' tests are again made for the first and'second variables to leanr whether they should be retained in the regression model. If their partial F's exceed the preselected level, they are retained; otherwise they are rejected. The procedure is continued and the next most highly correlated variable is entered into the regression. Significance tests a.re made as before and the method continued with each variable incorporated into the model in a previous step being tested. The method is terminated when all the variables have been considered and no more are rejected (cl. Draper and Smith (1966), p. 178-195for numerical example).

MO CALCULATIONSFOR SILICATE IONS

Rnnnnpwcns

1609

Ar,r,nw, L. C. (1970) Why three-dimensional Hiickel theory works and where it breaks down, 1z O. Sinanoglu and K. B. Wiberg, eds.,SigmntMolecular Orbital Theory. Yale Univ. Press, New Ifaven, Connecticut, ZZ7-245. (1972) The shape of molecules. Theoret. Chim. Acta 24, ll7-l}l. Al,unwurwourv, A, O. BesrreNsn, V. EwrNc, K. Ilnonnnc, eNn M. Tneorrnsnnc (1963) The molecular structure of disiloxane, (SiIL),O. Acta Chem. Scand. r7,2455-2t60. Awnnnsow, J. S., aNo J. S. Oconw (1g6g) Matrix isolation studies of Group-IV oxides. I. Infrared spectra a:rd structures of SiO, SirOr, and SLO".,1. Chem. Phgs. 5r,4189-4196. Anerr, T., ewn T. Zor,rar (1g69) Refinement of a coesite structure. Z. Kristal,Iogr. 129,381-387. Benrnr,l, L. S., L. S. Su, enn H. Yow (1g70) Leneths of phosphorus-oxygen and sulfur-oxygen bonds. An extended Hiickel molecular orbital examination of Cruickshank's d,rpn piclure. Inorg. Chem.g, 1908-1912. Bescu, 8., A. Vrsrn, exo H. B. Gney (1965) Valence orbital ionization potentials f rom atomic ryectra dala. T heor et. Chi,m.Ac t a 3, 459-464. Beun, Wnnxun (1970) Bond length variation and distorted coordination polyhedra in inorganic c-rystals.Trans. Amer. Crgstallngr.,4.ss. 6, 12b-15b. (1971) The prediction of bond length variations in silicon-orygen bonds. Arner. M'ineral. s6, lSZz-1599. Bnwt, H. A. (196S) Taqgent-sphere models of molecules: VI. Ion-packing models of covalent compounds. J. Chem. Ed.45,Z6g-728. Bonn, F. P., ervn W. N. Lrpscorus (196g) Molecular SCF calculations for SiII. and H"S. J. Chem. Plrys. So,98g-992. Borrr, N. G., arn Y. T. Srnucnrov (1g68) Structural chernistry of organic compounds of the nontransition elements of Group IV (Si, Ge, Sn, Pb). Zh. Struht.: Kluinu9,63M72 [transl. J. Struct. Chem. 9, 618-6Z2]. Boro, D. R., exo W'. N. Lrpscorrs (1g6g) Electronic structures for energy-rich phosphates.J. Theoret. BioI. 2s, 40Z4ZO. Bnoww, B. E., aNn S. W. Barr,ny (1964) The structure of maximum microcline. Acta Crystall.ogr. t7, l}gl-1400. Bnowr, G. E., eNn G. V. Grsss (196g) Oxygen coordination and the Si-O bond. Amer. Mi,neral. s4, l128-l1zg. -, (1970) Stereochemistry and ordering in the tetrahedral porAND tion of silicates. Amer. Mineral.55, 15gZ-1607. aNn P. H. Rrnnu (1969) The nature and variation in length of the Si-O and Al-O bonds in framework silicates. Amer. Minerar. 54, 1044-1001. BusrNo, W. R., aNn II. A. Lnw (1964) The effect of thermal motion on the estimation of bond lengths diffraction measurements. Acta Crystallogr. 17, 142146. CeruunoN, M. (1971) The Crystal Clrcmi,strg ol Tremolite anil Richteri,te: A Studg of Selected, Anion and, Cati,on &tbstituti.on. Ph.D. thesis, Virginia Polytechnic Institute and State University, Blacksburg, Virginia. CaNwrr,r,o,E., G. Rossr, eNn L. Urvcennru (1968) The crystal structure of macdonaldite. Accad,.N,az.Lincei 4s,gW4L4. CmuoNrr, E., aro D. L. R"rruornr (1968) Atomic screening constants from SCF functions. .I. Ch em. Phgs. 38,2686-2689.

1610

GIBBS, HAMIL,

LOAISNATHAN,

BARTELL,

AND YOW

Cooe, A., A. Der, Nncno, ewn G. Rossr (1967) The crystal structure of krauskopfite. .dccod.Naa. Dei, Lincei 42,859-873. Corr,rr.rs,G. A. D., D. W. J. Cnurcrsnewr, eNn A. Bnnuzn (1972) Ab i,nitio calculations on the silicate ion, orthosilicic acid and their Zr, a X-ray spectra. J . C hern. Soc., F aradny Trans. I I, 68, I 189-1195. CmtoN, A. F., awo G. Wrr,rrNsor.r (L969) Ad.uam,ed, Ircrgoni'c Chemistra. John Wiley and Sons,New York, N. Y. Corrr,sor.r, C. A. (1939) The electronic stmcture of some polyenes and aromatic molecules. VII. Bonds of fractional order by the molecular orbital method. Proc. Rogal Soc.,Ser.A,169,413-428. CnurcrsnaNr, D. W. J. (1961) The role of 3d-orbitals in r-bonds between (a) silicon, phosphorus, sulfur, or chlorine and (b) oxygen or nitrogen. J. Chem. Soc.7077,5486-5504. Der,r,rxca, G., eNo P. Ross (1968) Semi-empirical prediction of bond lengths and conformations . R ec. Trau. Chi,rn. 87,906-915. Donn, C. G., ewo G. L. Gr,nll (1969) A zurvey of chemical bonding in silicate minerals by X-ray emission spectroscopy. Amer. Mi.neral. 54, 1299-l3ll. Dor,rAsn, W. A. (1965) Reinvestigation of the structure of low cristobalite. Z. Kristallo gr. 721, 369-377. (1968) Refinement and comparison of the structures of zoisite and clinozoisite. Amer. M,i,nerar. $, 1882-1898. (1969) Crystal structure and cation ordering of piedmontite. Amer. Mineral. 54,71tu_-717. (1971) Refinement of the crystal structures of epidote, allanite and hancockite. Amer. M ineral. 56, 447464. DoNNev, G., rwo R. Ar,r,rvrew(1968) SLOrc groups in the crystal structure of ardennite. Acta Crystallngr. B24, 845-855. Dnarnn, N. R., exr I[. Surrn (19ffi) AWIieiI Regression Analysis. John Wiley and Sons,fnc., New York. Frrcnn, L. W. (1969) The crystal strusture of grunerite. Mineral. Soc. Amer. Spec.Pap.2, 95-100. (1970) Refinement of the crystal structure of anthophyllile. Carnegie Inst. W aslui,ng ton Y ear B ooh, 68, 283-288. Frscnnn, K. (1969) Yerfeinerung der Kristallstruktur von Benitoit BaTitSilOJ. Z. Kristall,o gr. 729,369-377 . Fnnno, R. L., eNr D. R. Poecon (1969) Determination and refinement of the crystal structure of margarosanite, PbCaoSi*;On. Z. Kristallngr. 728,213-228. Fyru, W. S. (1954) The problem of bond !,ype. Amer. M'ineral.39, S1-1004. Gevrw, R. M., Jn. (1969) Simplified molecular orbital approach to inorganic stereochemistry. J. Chetn. Ed. 46,413422. Gruus, G. Y. (1966) The polymorphism of cordierite. I, The crystal structure of low cordierite. Amer. Mi,nerar. 51, 106&1087. (1969) Crystal structure of protoamphlbole. Mi'neral. Soc. Amer. Spec, Pap. z, l0l-109. D. W. Bnocx, eNo E. P. Mnecnnn (1968) Structural refinement of hydrous and anhydrous synthetic beryl, AL(Be"Si")Oreand emerald, Al'.nCr".'(Be"Si')Or. Lithos, 1,275-285. Grr.r,nsrrc, R. J. (1960) Bond angles and the spatial correlation of electrons. J. Amer. Ch.em.Soc.82,5978-5983. Gnrrrrtn, W. P. (1969) Raman studies on rock-forming minerals. Part 1. Orthosilicates and cyclosilicates.J . Chem.Soc. (A), 1372-L377 .

MO CALCULATIONS FOR SILICATE

IONS

1611

Eeuu,, M. M., G. Y. Grsss, ewo P. H. R"rsse (1971) The location of the hydrogen atoms in the water molecule of dioptase. [abstr.]. Geol. Soc. Amer. Abstr. Programs,3, 315. -, G. V. Grsns, L. S. Benrnrr,, eNn I[. Yow (1971) A comparison of Si-O bond lengths wiih EIIMO bond overlap populations. [abstr.]' Geol. Soc. Amer" Abstr. Programs, 3, 589. Horrrvreww, R. (1963) An extended Eiickel theory. I. Ifydrocarbons. J. Ch'em. Phgs.39, l3W-L412. Laucnorv, R. B. (1971) The crystal stmcture of kinoite. Amer. MhwraL 56, 193-200. Lezennv, A. N. (1964) Polymorphism of molecules and complex ions in oxygen compounds of silicon and phosphoms. Report 1. Nature of the Si-O-Si bonds and values of the valence angles of oxygen. Izu. Akail. iVauk ,$SSE, Ser. Khi/m.2.235-241. Lmueu, F. (1961) Untersuchungen iiber die Griisse des Si-O-Si Yalenz-winkels. Acta Crgstallogr.14, 1103-1109. LoursxerneN, S. J., awo G. V. Grsns (1971) A comparison of Si-O distances in the olivines with the bond overlap populations predicted by the extended Hiickel molecular orbital (EHMO) theory. [abstr.]. GeoI.$oc. Amer. Abstr. Prog:rams,3,686. (1972a) The efrect of tetrahedral angles on Si-O bond overANDlap populations for isolated tetrahedra. Amer. M,i,neral s7,16l+-1642. (1972b) Variation of Si-O distances in olivines, soda melilite AND-and sodium metasilicate as predicted by semiempirical molecular orbital calculations. Amer. M ineral. 57, 1643-1663. (1972c) Aluminum-Silicon distribution in znnyite. Arner. AND Mineral. s7, 1068-1087. (1972d) The Si-O bond length variation in pyrosilicates. AND Amer. Abstr. Prograrns,4,580-581. labstr.l GeoI. Soc. aNu J. V. Surrn (1971) Crystal structure of tilleyite: Refinement and coordination. Z. Kri*tallo gr. 132,288-306. McDoNer,o, W. S., exn D. W. J. Cnurcrsrrexr (1967a) A reinvestigation of the structure of sodium metasilicate, Na"SiO". Acta CrystalX.ogir, 22, 3743. _ (1967b) Refinement of the structure of hemimorphite. z. AND _ Kris tallo gr. 124, 180-191. Meagher, E. P. (1967) Polym,orphism ol Cord:ieri,te. Ph.D. thesis, Penn. State University, University Park, Pennsylvania. Mrtcnnll, J. T., F. D. Br,oss, ervn G. V. Grsss (1971) Examination of the actinolite structure and four olher C2/m a.mphiboles in terms of double bonding. Z. Kri*tall,ogr. 133,?73-300. Mrrcnnrr,, K. A. R. (1969) The use of outer d orbitals in bonding. Chem. Rea.69, 157-r78. Mur,r,rrow, R. S. (1955) Electronic population analysis on LCAO-MO molecular wave function s. l. J. C hem. Phgs. 23, 1833-1846. Nor,r,, W. (1956) Characteristika der Siloxan-bindung in polymeren Anionen (Silikaten) und polymeren molekiilen (Siliconen). Fortschr. Mirrc,ral. 34, 63-&1. (1968) Chemistry and, Technologa of Si.Itcunes, 2nd ed.. Academic Press, Ine., New York, N.Y. OmnueMrtnn, I{. (1972) The molecular structures of cyclosiloxanes. latrstr.] Fowth Austi,n Sym.posium on Gs,s Phase Molewlar Structure, Ll-12.

t6l2

GIBBS, HAMIL,

LOAISNATHAN,

BA&TELL,

AND yOW

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MO CALCALATLONS FOR SILICATE IONS

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YnnuoocnN, J. (1953) Physical properties and bond type in Mg-Al oxides and silicateir.Amer. M'ineral. $, 5EZ-879. Wrnnren, D. J., elln G. SrrmoNs (lg72) Elastic properties of alpha quartz and the alkali halides based on an interatomic force model. J. Geophus. Res.77, 826-856. Wor,rsnunc, M., eNn L. Hnr,lrnor,z (19b2) The spectra and electronic structure of the tetrahedral ions MnOr-, CrOn- and CIO;. J. Ch,em.Ph,ys. 20,837-843. Zecnanresow, W. H., aNn H. A. Pr,orrrxcEn (1965) Extinction in quartz, Acta Crystallo gr. tB, 7l0-7 14. Manuscrtpt recei,ued,Janunry 11, 197P; accepted,tor publi,cati,on,Jw,e 6, 1n2.

Note add,eil i,n proof ba GVG: The electrostatic valence rule proposed by Pauling (1929) and extended by Baur (1970) was originally.conceivdd to chaftircterize strengths of ionic-type bonds and local charge balance in stable iohic crystals. It is evident, however, that the model seems to apply equally well to compounds in which the bonds have a relatively large arriount of covalent character. For these compounds,Pauling (1960,S4Z-548, Foohrote 64) has indicated that "if the bonds resonate among the alternative positions, the valence of the metal atom will tend to be divided equally among the bonds to the coordinated atoms, and a rule equivalent to the electrostatic valence rule would express the satisfaction of the valences of the nonmetal atoms.', Pauling,s statement implies [1] that the strength of an electrostatic bond, s, can be equated with bond number, rz (Pauling, 1947,J. Amer. Clrcm. Soc. 69, 542-559); t2l that the correlations between f (O) and the length of the Si-O bond (Smith, 1953,Amer. Mineral. 38, 643-661; Ba-ur, 1970) are similar to the well known bond-length bond-number curve for carbon-carbonbonds; and t3l ihat the chargeson bonded atoms are small in agreement with his electroneutrality principle (Pauling, 19ffi, General Chemistry, W. II. Freeman and Co.,286-287). The inference that z and s are equivalent is consistent with the observation ihat f(O) and z(Si-O) are inversely correlated (Louisnathan and Gibbs, l972b). Although Baur calls his model the extended electrostatic valence rule, he is careful to note that the correlation between observed Si-O bond length and f(O) could be interpreted in terms of Cruickshank's (1961) double bonding model as well as the Born model for ionic crystals.