Chapte3

r
Characteristicsof energy surfaces

3.1 Strategiesfor geometry optimization

The extension of the harmonic and Morse vibrational models to poly-
atomic moleculesrequiresthat the multidimensionalenergy surfacebe
analyzedin a mannerthat allows one to approximatethe molecule,smo-
tions in terms of many nearly [Link] this section,we
will explore the tools that one uses to carry out such an analysisof the
surface.

Many strategiesthat attemptto locateminima on nrolecularpotentialen-

ergy landscapesbegin by approximatingthc pcltentialener-syV for gcornetries
(collectivelydenotedin termsof 3A cartesiancoordinares
{qr})in a Taylorse-
riesexpansionaboutsonre"startingpoint" geometry(i.e..the currentnrolecular
geometryin an iterativeprocess):

I ' ( q r ) : I 1 ( 0 ) +t ( a r l o q ^ ) q+t t l 2 l o i H i . * 4 ** . . . . (3.1)

H e r e .i ' ( 0 ) i s t h e e n e r g y u * , nl u. r r " n r r e o n . ] e t rtyU,r, , t O , ^ l : 9 1 i s r h e - e r a d i e n t o f

t h e e n e r g y a l o n g t h e cqoao r d i n a t eH,1 . s= e 2 I / l d q i a q k )i s t h e s e c o n d d e r i v a t i v e
or [Link] thelengthof the"step"to be takenalongthiscartesian
[Link] exampleof an energysurfacein only two dinrensions is given
in Fig. 3.1 wherevariousspecialaspectsare [Link] [Link]
correspondingto stablemolecularstructures,transitionstates(first ordersaddle
points)[Link].
If the only knowled-qethat is availableis l'(0) and the gradientcoruDonents
(e.g..computation ofthesecondderivatives is [Link] morecomputationally
taxing than is evaluationof the gradient),the linear approxirnation

I ' ( q i ) : r t t l )+ S^qi (3.2)

f

suggests thatoneshouldchoose"step"elementsq1 thatareoppositein signfrom

that of the corresponding
gradientelementsgr : (a vloqr). The magnitudeof

104
 S t r a t e g i e sf o r g e o m e t r yo p t i m i z a t i o n 1n6

Secondorder saddlepoint
TransitionstructureA

Minimum for
productA

-0.5
Sccondorder imensional
0.5
saddlepoint potentialsurface
(r.) Valley-ridge s h o w i n gm i n i m a ,
- tr-) inflectionpoint
Minimum lor reactant transitionstates,and
_ - l
p a t h sc o n n e c t i n gt h e m .

thestepelementsis usuallykeptsmallin orderto remainwithin the "trust radius"

within which the linearapproximarionto z is valid to someprederermined
desired
precision.
when secondderivativedata is available,there are diIl-erentapproachesto
predictingwhat step lqrl to take in searchof a minimum. we first write the
quadraticTaylor expansion

I ' ( , t t =t I ' r 0 r+
f g ^ V -r l , 2 l l , H,.+,tt (3 . 3 )
k r."

in matrix-vectornotation

t t ( q ) =L , ( o ) + q r . +g t l 2 q r . H . q (3.4)

rvith the elements{q1

} collectedinto the column vectorq whosetransposers
denotedqr. Introducingthe unitarymatrix u that diagonalizesthe symmetricH
matrix,the aboveequationbecomes

rG): I r ( 0 1 +g r u u r q + t T 2 q r u u r H u u r q . (3.5)

BecauseUrHU is diagonal,

( u r H u ) r 1: 8 r . r i r (3.6)

and haseigenvalues )"[Link] non-linearmolecules,3r/ - 6 of theseeigenvalues

rvill be non-zero;for linear molecules,3,A/- 5 will be [Link] 5 or 6 zero
eigenvalues of H haveeigenvectorsthat describetranslationand rotationof the
entiremolecule;they are zero becausethe energysurfacez doesnot changeif
the moleculeis rotatedor [Link] eigenvectorsof H form the columnsof
tuo C h a r a c t e r i s t i cosf e n e r g ys u r f a c e s

the array U that brings H to diagonallorm:

1-1.7)

[Link] define

Q,:lL,[,,,qr and G,:lL' , ! ^, g r (i 8)

to be the componentof ,n.*r,"p {qp} and of tn. [Link] along the rrth ergen-
vectorolH. the quadraticexpansionof l,'canbe u'rittenin termsof stepsalong
the 3,\ - 5 or 3t/ - 6 {Q,,,} directionsthat correspondto non-zeroHessian
eigenvalues:

v(qt): r'(0)+ t cl,e,,+ 112Le,,,)",,,e,,,. (3.r.r1

The advantageto transformingtlie gradient,[Link] to the eigenmode

basisis that eachsuchmode (labelednr) appearsin an independent uncoupled
form in the expansionof /. This allou's us to take stepsalong eachof the Q,,,
directionsin an independentmannerwith eachstepdesignedto lowerthepotential
ener-qy(aswe searchfor rninima).
For eacheigenmodedirection,one can askfor u&at stepp u'ouldthe quantity
G Q + I12),Q2 be a [Link] quadraticform with respect
to Q andsettingthe resultequalto zero gives

Q r ,= - G , l ) ' r , , (3 10)

but with a rnagnitudegiven

that is, [Link] a stepoppositethe _eradient
by the gradientdivided by the eigenvalueof the Hessianmatrix. lf the current
moleculargeometryis one that hasall positive/.,,,values,
this indicatesthatone
may be "close" to a minimum on the energysurface(becauseall i,,, arepositive
at minima).In sucha case,the step Q,,: -Gu,/i,,, is opposedto the gradient
along ali 3l/ - 5 or 31y'- 6 [Link] energychangethat is expectedto
occurif the step{p,,,} is takencanbe computedby substitutingp,, : -G,,/L,,
into the quadraticequationfor /:

/(afterstep): I,'(0)+ | Cl1-C,, l\,,) * 1 l2LL,,,(-G,,, 1I,,,)2

"'
: r(o)- r)z)- ).n,(--G,,,f),.,,)2. ,r.,,,

"downhill"
This clearlysuggeststhat the stepwill lead in energyas long asall of
the ).,,,valuesare positive.
However,if one or more of the ),n,arenegativeat the currentgeometry'. one is
in a regionof the energysurfacethatis not closeto a minimum. In fact,if only one
),,, is negative,onq anticipatesbeing neara transitionstate(at which all gradient
componentsvanishandali but one.i.n,arepositivewith one i.o,negative).In such
 S t r a t e g i e sf o r g e o m e t r yo p t i m i z a t i o n
107

a [Link],'e
analysissuggests a step0/,r : -G,,/Ln, aloneall of the
takin_q
modes havingpositive).,,,,
but takin-e
a stepof oppositedirectione,, J +G,
1).,
alongthedirectionhavingnegarivel,?.
In [Link] stephasbeensuggested within the eigenmodebasis,one
needsto expressthat step in terms of the original cartesian coordinatesq1 so
thatthesecartesianvaluescan be alteredwithin the softwareprogramto effect
the predictedstep. Given valuesfor the 3N - 5 or 3l/ - 6 stef components
Q,, @.b..the stepcomponenrsQ,,, alongthe 5 or 6 modeshavinj zero Hessian
eigenvalues canbe takento be zerobecausethey would simply translate
or rotate
themolecule),onemustcomputethe{q1,}.To do so,we usethe relationshin

Q,:\ui, a1r (3.r2)

and"vrireits inverse(usingthe unitary natureof the u matrix):

qr:L,L1t.,,,Q,,, (3.1i)

to computethe desiredCartesianstepcomponents.
In usi'g the Hessian-based
approaches
[Link] takespecial
carewhenone or moreof the Hessianei-senvaluesis [Link] oftenhappens
wnen:

(i) onehasa molecuie "softrnodes"

containing (i.c.,de_urees
of tieedomalonglvhich
[Link]
little).or
(ii) onemovesfrorna regionofnegatir,ccur\arureintoa regionofpositivecur'ature
(orviceversa)
- in suchcases,
[Link] or nearzero.
For [Link] expressiofl
e,,: -G,,/n,, can producea yerv lar-9e
stepalong the mode havingsmall [Link]
must be takento not alrow
suchincorrectartiliciallylargestepsto be taken.
Beforeclosin-e thissection.I shouldnotethatthereareotheri'portant
regions
of potentialener-qy surf-acesthat one must be able to locateand characterize.
Above""vefbcusedon locarrninimaa'cl transition
[Link] Chapterg, we will
discusshow to follow so-cailedreactionpathsthat
connectthesetwo krndsof
statlonarypoints using the type of gradienta'd
Hessianinformationthat ,"ve
introduced earlierin this chapter.
[Link] is sometirnesimportanrto find
_qeomet'es at which two Born-
oppenheimerener-qysurfacesI"1(q) and z1([Link].
First. ret'sspenda fer.v
minutesthinkingaboutwhethersuchsurfacescan
rndeedintersect, becausestu-
dentsofte' hear that surf'acesdo not intersect
but. insteaclundergo..avoideci
crossings".To understandthe issue,let us assume
that we havetwo [Link] func_
ttons@1and @2bothof rvhichdependon
3,v - 6 coordinates {q}. Thesetwo
ftrnctionsare not assumedto be exactei-eenfunctions
of the HamiltonianF1.
but likely are chosento approximate sucheigentunctions. To find the improved
108 C h a r a c t e r i s t i cosf e n e r g ys u r f a c e s

functionsV1 and W2that more accuratelyrepresentthe eigenstates.

one usually
forms linear combinationsof (D1 and (D2,

V,r:[Link] *C,r'.:O: ( 3r. 4 )

from which a 2 x 2 matrix eigenvalue problem arises:

Ht: - E Ht.:
(3.r5)
Htt Hz2 - E

This quadraticequationhas rwo solutions

2En : 1.11r.'
+ H2.2)
+ ( 3 r.6 )
Thesetwo solutionscanbe equal(i.e.,thetwo stateenergies cancross)only if the
squareroot factor [Link] factor is a sum of two squares(each
thus being positivequantities),this can only happenif two identitieshold:

Htt: H:.: ( 3 r.7 )

and

H r . :: o . (3.18)

The main point then is that in the 31/ - 6 dimensionalspace,the two [Link]
generallynot have equal [Link] a spaceof two lower dimensions
(because therearetwo conditionsthat must simultaneousll'be obeyed- Hr.t :
H22and Ht.2 :0), theirenergies maybe [Link] not haveto be equal,but
it is possiblethat they [Link] is basedupon suchan analysisthat one usuallysays
that potentialenergysurfacesin 31/ - 6 dimensionsmay undergointersections
in spacesof dimension3N - 8. If the two statesare of different [Link]
off-diagonalelement111.2 vanishesautomatically,so only one otherconditionis
neededto [Link], we saythat two statesof differentsymmetrycan
crossin a spaceof dimension3N - 7.
To find the lower-dimensionalspacein which two surfacescross,one must
have availableinformation about the gradientsand Hessiansof both functions
V1 and,V2. One then usesthis information to locate a geometryat which the
differencefunction F : f\ - vil2 passesthrough zero by using conventional
"root
finding" methodsdesignedto locatewhereF : 0. once onesuchgeomerry
(qe) has been located,one subsequentlytries to follow the .,seam"along which
the function F remainszero. This is done by parameterizingstepsaway from
(qo) in a manner that constrainssuch stepsto have no componentalong the
gradientof F (i.e.,to lie in the tangentplanewhere F is constant).For a system
rvith 3N - 6 geometricaldegreesof freedom,this seamwill be a sub-surface of
lower dimension(31/ - 8 or 31/ - 7 as noted earlier).such intersectionseam
locationproceduresarebecomingmore commonlyemployed,but are still under
 N o r m a lm o d e so f v i b r a t i o n 109

very [Link] an importantingredient

rvhenoneis interestedin studying,for example,photochemicalreactions
in rvhich
the reactantsand products may move from one electronicsurfaceto another.

3.2 Normal modes of vibration

H a v i n gs e e nh o w o n e c a n u s e i n f o r m a t i o na b o u t t h e g r a d i e n t sa n d H e s -
sianson a Born-oppenheimersurfaceto locategeometriescorrespond-
ing to stablespecies,let us now move on to see how this same data are
usedto treat vibrationson this surface.

For a polyatomic molecule whose electronic energy dependson the 31y'

cartesiancoordinatesof its N atoms,the potentialenergy z can be expressed
(approximately)in terms of a Taylor seriesexpansionabout any of the local
[Link] course,difrerentlocal minima (i.e., differentisomers)will have
difl-erentvaluesfbr the equilibrium coordinatesand for the derivativesof the
energywith respectto [Link] Taylor seriesexpansionof the
electronicenergyis written as

v ( q * ) = l , 1 o l + f t a I l i ) q 1 ) q+pt l 2 L q , H 1 r . Q t * . . . , (3.19)
k j.k

ivherez(0) is thevalueof theelectronic energyat thestablegeometryunderstudy,

q1 is the displacement of the kth cartesiancoordinateawayfrom rhis starting
position.('dI"laqk) is the gradientof the elecrronicenergyalongthis direction,
andthe H 1.t;arethe secondderivatileor Hessianmatrixelements alongthesedi-
rections,H i.r : G2V lAq iAqk).If the geometrycorresponds to a stablespecies,
thegradienttermsrvill all vanish(meaningthis geometrycorresponds to a min-
tmum,[Link] saddlepoint).and the Hessianmatrix will possess 3rv - 5
(for linearspecies)or 3N - 6 (for non-linearmolecules)positiveeigenvalues
and5 or 6 zeroeigenvalues (corresponding to 3 translational
and2 or 3 rotational
motionsof,themolecule).If the Hessianhasonenegativeeigenvalue, the geom-
etry correspondsto a [Link] now on, we assumethat the
_qeometry
under sfudy correspondsto that of a stableminimum about which vibrational
[Link] treatmentof unstablegeometriesis of great importanceto
chemistry. bLrtthis materialwill be limitedto vibrationsof stablespecies.

3 . 2 . 1T h e N e w t o ne q u a t i o n so f m o t i o n f o r v i b r a t i o n
Thekineticand potentialenergymatrices
Truncatingthe Taylor seriesat the quadraticterms (assumingtheseterms dom-
inatebecauseonly small displacements from the equilibriumgeometryare of
110 C h a r a c t e r i s t i cosf e n e r g ys u r f a c e s

interest),onehasthe so-calledharmonicpotential:

t' (qr) = t' ((\ + \ l2lt1 i H i r,c/t (3 . 2 0 )

1.i

The classicalrnechanicalequationsof motionfor the 3N{r77,}

coordinatescanbe
written in termsof the abovepotentialenergyand the follou'ingkineticenergy
function:

T - 1 /) \-,,, ' '. t; t: ( 3 . 2t1

/-"'

where ri7 denotesthe tirnerateof changeof the coordinateq i andtn, is the mass
of the atomon [Link] Cartesiancoordinateresides.
The Neu,tonequations
thus obtainedare

nt,i-*lHrr,4t i l 1 ) t

wherethe forcealongtheTthcoordinateis givenby rninusthe derir.'ative of the

potentialI,' along this coordinarc(AI/ldq i): l* H [Link].r,ithinthe harntonic
[Link].
Theseclassical equations canmorecompactlvbeexpressed in termsofthetime
evolutionof a setof so-calledmassweightedCartesiancoordinates definedas

xi:[Link])12. r l l l r

in terms of which the aboveNeu'tonequationsbecome

i',:-Lr',.^r^ (3.24)
k

and the mass-weighted

Hessianmatrixelementsare

H l . 1: H i . r \ t , , rtt) - t ' 2. (3.25

)

The harmonic vibrational energies and normal mode eigenvectors

Assumingthat the rl undergosomeform of sinusoidaltirneevolution:

) it ( t ) : - r , ( 0c) o s ( o / ) , (3.26)

and substitutingthis into the Newton equationsproducesa matrix eigenvalue

equation:

-2xy:lu',.rxt \ 3 . 2|7

in which the eigenvalues

arethe squaresof the so-callednonnal modevibrational
frequenciesandthe eigenvectors give the amplitudesof motion alongeachof the
31y'mass-weightedCartesiancoordinatesthat belong to eachmode. Hence,to
perform a normal-modeanalysisof a molecule,one forms the mass-weighted
tr
ffi'
N o r m a lm o d e s o f v i b r a t i o n 111
,

- -
Hessianmatrix and thenfindsthe 3N 5 or 3N 6 non-zeroeigenvalues cor2
as
rrellas the corresponding eigenuectors
-tf'l).
\\'ithin this harmonictreatmentof [Link] total vibrational
energl'ofthe rroleculeis givenas
l.\ -5 or 6
E { r ' 1 . r ' . . . . . . v :i o\ r r ) = t/ h' *t t,\ t' ,1 l vt l ' 2 t (3 . 2 8)

- -
a sum of 3,V 5 or 31y' 6 independent contributions.
one for eachnormal
[Link] corresponding
total vibrational
wave function

qr: ./,,(,,,,) (3.29)

ll
/=l.l\,5 or6

isa productof 3N - 5 or 3N - 6 harmonicoscillatorfunctionsly',.(.r{l)),onefor

[Link] energygapbetweenone vibrationallevelandanotherin
whichoneof the vl quantumnurnbers by unity(i.e..for fundamental
is increased
t
r ibrationalr a n s i t i o n
) s
i s

(3.30)

Theharmonicmodel thus predictsthat the "fundamental"(rr - 0 --->r.': I ) and

"hotband"(u : I + v : 2) transitions
shouldoccurat [Link]
o!ertone(t, : 0 + l : 2) transitions
shouldoccurat exactlytwice this energy.

3 . 2 . 2T h e u s e o f s y m m e t r y
Symmetryadaptedmodes
Water
It is often possibleto simplity the calculationof the normal mode frequencres m o l e c u l es h o w i n gi t s
andeigenvectors by exploitingrnolecularpoint [Link] molecules t w o b o n d l e n g t h sa n d
thatpossesssymmetrvat a [Link] electronicpotential b o n d a n g l e .
tr1(r7r)displayssymmetrvwith respectto displacements of symmetryequir.a-
lentCartesiancoordinates. For [Link] watermoleculeat its C2u
equilibriumgeornetryas illustratedin Fig. 3.2. A very small movementof the
H2Omolccule'slefi H atomin the positive-r direction(A-t1-)producesthe same
changein the potentiali/ as a correspondingly smalldisplacernent of the right
H atomin the negativc,tdirection(-A-rR).[Link] the left H in
thepositive_r'direction(A.v1)produces an energychangeidenticalto movement
of the right H in the positive,r'direction(A_r,n).
Theequivalcnce of thepairsof Cartesiancoordinatedisplacements is a resultof
thetact that the displacementvectorsareconnectedby the point groupoperations
of the C:, gror-rp. In [Link] Arlthrough the r,: plane(the two Two planes
planesare depictedin Fig. 3.3) [Link], and reflectionof Ars through of symmetry of the
thissameplaneyields A.r'R. w a t e rm o l e c u l e .
I tz C h ar a c t e r i s t i cosf e n e r g ys u r f a c e s

Moregenerallr''. it is possibleto combinesetsof cartesiandisplacernent coordi-

n a t e s{ r 7i1i n t o s o - c a l l e d s y m m e r r y a d a p t e d c o o r d i ' a t e s
{ e r . i ) , u , h e r e t h e i n d efx
labelstheirreducible representation in theappropriate poinlgroupand.7labelsthe
particularcombinationof that [Link]
adaptedcoor<Jinates
can be formed by applyingthe point group prqectron operators(that
are treated
in detailin chapter4) to the indi'idual cartesiandisplacenient
coordinates.
To [Link] H2o nroleculein the coordinate
svsterncle_
[Link] 3N:9 massu'eightedCartesian<.lisplacement
coordinates
( X r _ .l ' r _Z
. t . X o . f ' o . Z o . . l n , l n . Z { c a n b e s y m n r e t r y a d a p t ebcl l, a p p l l , r n g t h e
following4 projectionoperators:

Pu,:)*o,.+o,,*C;. ( 3 . 3I t
Pt,, : I f 6r,. -o.., - C':. (3.31r
Pt,,: l-o,.* o., -C:. ( 3 . 3)3
% : : 1 - o , , - { , ,* C . . ( 3 . 3)4

to eachof the 9 originalcoordinates (the symbolo denotesreflectionthrough

a plane and c2 meansrotationaboutthe molecules C2 axis).
of [Link]
v'ill not obtain 9 x 4 : 36 independentsymmetry adapted
coordinatesin this
manner;man1,identicalcombinations will [Link] 9 will be independent.
Theindependent combinationsof c 1srvtnrctn.(normalizedto produce'ectors
of unit len_eth)
are

Qut.r=2r":Jf;-)fp1. (3.3
5)
Qo'.:.=Z'"Iii+ln]. (3.36)
? . , . - :: [ f o ] . 13171

Thoseof b2 symmerryare

Qbrr=2'/t[Xy+Xp.l. (3.8
3)
Q v z : 2 - t i 2 7 Y y- Y p l , (3.39)
0u,: : [Xo]. (3.40)

and the combinations

9 b , . ,= 2 - ' / ' l z t + Z p . l (3.1r)

Qa,t = lZol (.3.42)
are of b1 symmetry,whereas

Q o r . ,: 2 - r / 2 1 7 y - Z u ) (3.43)

is of a2 symmetry.
 Normalmodesof vibration 113

Pointgroup symmetry of the harmonic potential

Thesenine Qr.i areexpressed
asunitarytransformations
of theoriginalmass-
Cartesian
rveighted coordinates:

Q r . ,: L C r . , . , , ' Y r (3.44)

Thesetranstbrmationcoefficients{[Link]} can be usedto carry out a unitary

transformationof the 9 x 9 mass-weighted
Hessianmatrix. In so doing,we need
only form blocks

Hi., : y. (nt r, )'''t C r., r (3.15)

L, C 11 H1,.1,'1,m

rvithin which the symmetriesof the two modes are [Link] off-diagonal
elements

pt y )-t i' Cy.1.y

Hi.l' = L Cr.,.rHr.r,(m (3.46)

vanishbecausethe potentialV(qi) (and the full vibrationalHamiltonianH :

T + V) commuteswith thc C2, pointgroupsymmetryoperations.
As a result,the 9 x 9 mass-weighted Hessianeigenvalue probler.n
canbe sub-
dividedintotwo 3 x 3 matrixproblems(of ar andb: symmetry),one2 x 2 matrix
of b1 symmetryand one I x I matrixof a1 [Link] eigenvalues of each
of theseblocksprovidethe squares of the harmonicvibrationalfrequencies. the
eigenvectorsprovidethe normalmodedisplacements as linearcombinations of
thesymmetryadapted{Qr. il.
Regardlessof whether symmetry is used to block diagonalizethe mass-
weightedHessian,six (for non-linearmolecules)or five (for linearspecies)of
theei-eenvalues will [Link] eigenvectorsbelongingto thesezeroeigen-
valuesdescribethe thrcetranslations and two orthree rotationsof the molecule.
Forexample,

I
(3.,17)
*lS1*Xp*-{ol.
I
(3.,18
)
*[Yt+]h*rol'
I
(3.,+9)
*tzt*ZP.*Zo)
arethreetranslationeigenvectors
of [Link] and bl Symmetry,and

I
- (/ aZ r - Zr<) (3.50)

ts a rotation(aboutthe _r,-axis
in Fig. 3.2) of a2 [Link] rotationvector
canbe generatedby applyingthe a1projectionoperatorto ZL or to Zp. The other
 C h a r a c t e r i s t i cosf e n e r g ys u r f a c e s

Symmetric
and asymmetricstretch / tn.'.
m o d e sa n d b e n d i n g
mode of water.
O
,/"

Symmetries
of vibrationsof
methane.

two rotationsare of b1 and bt symmetry and involve spinningof the molecule

aboutthe,t- and:-axesof Fig. 3.2,respectively.
So,of the nine Cartesiandisplacements,threeareof a1symmetry,threeof b2.
two of br. and one of [Link] these,thereare threetranslations(a1,b2, and b1)
and threerotations(bz,bt, and a2).This leavestwo vibrationsofal and one of
b2 synmetry. For the H2O exarnpletreatedhere,the threenon-zeroeigenvalues
of the mass-weightedHessianare thereforeof a1, b2, and a1 [Link]
describethe symmetricandasymmetricstretchvibrationsandthe bendingrnode,
respectively,as illustratedin Fig. 3.4.
 N o r m a l m o d e so f v i b r a t i o n 1't5

Themethodofvibrationalanalysispresentedherecanwork for anypolyatomic

[Link] knows the mass-weightedHessianand then computesthe non-
zeroeigenvalues. which thenprovidethe squaresof the normal modevibrational
frequencies. Point
groupsymmetrycanbe usedto blockdiagonalize thisHessian
and to the
label vibrationalmodesaccordingto symmetryas we showin Fig. 3.5
for the CHa moleculein tetrahedralsymmetry.