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Statistical�
mechanics of quantum-classical systemsSteve�
Nielsen and Raymond KapralChemical Physics Theory Group, Department of Chemistry, University of Toronto,Toronto, ON M5S 3H6, Canada
Giovanni�
CiccottiINFM�
and Dipartimento di Fisica, Universita ‘‘La Sapienza,’’ Piazzale Aldo Moro, 2, 00185 Roma, Italy�Received�
29 May 2001;accepted13 July 2001�The statisticalmechanicsof systemswhoseevolution is governedby mixed quantum-classicaldynamics�
is investigated.The algebraicpropertiesof the quantum-classicaltime evolution ofoperators� andof thedensitymatrix areexaminedandcomparedto thoseof full quantummechanics.Theequilibriumdensitymatrix thatappearsin this formulationis stationaryunderthedynamicsanda methodfor its calculationis presented.Theresponseof a quantum-classicalsystemto anexternalforce
which is appliedfrom the distantpastwhenthe systemis in equilibrium is determined.Thestructure� of the resulting equilibrium time correlation function is examined and thequantum-classical� limits of equivalentquantumtime correlationfunctionsarederived.The resultsprovide a framework for the computationof equilibrium time correlation functions for mixedquantum-classical� systems. © 2001
�American Institute of Physics. � DOI:
�10.1063/1.1400129�
I.�
INTRODUCTION
Often�
situationsarise where it is appropriateto studycomposite� dynamicalsystemswith interactingquantumme-chanical� andclassicaldegreesof freedom.In condensedmat-ter�
physicssuchsituationsoccur when one is interestedinthe�
dynamicsof a light quantumparticle or set of quantumdegrees�
of freedom interacting with more massiveparticles. 1–3 Specific
�examplesincludeproton transfer,4
�sol-�
vation� dynamicsof an excesselectron,5�
and nonradiativere-laxation�
processesof moleculesin a liquid-state environ-ment.� 6
�In�
thesecircumstancesit is not feasibleto attemptafull quantumsolution of the Schrodinger
�equationfor the
entire� system.Consequentlyone is led to considerthe dy-namics� of a quantumsubsystemcoupledto a bathwheretheenvironmental� degreesof freedom are treated classically.Such�
mixed quantum-classicalsystemsarise in other con-texts�
aswell.7
Dif�
ferent formulationsof the dynamicsof such mixedquantum-classical� systemshaveappearedin the literature.Inthese�
reduceddescriptionsof the quantumdynamicsthe en-vironmental� degreesof freedom are accountedfor by theinclusion!
of dissipativeand decoherencetermsin the equa-tions�
of motion,8–10 through�
multistate Fokker–Planckdynamics� 11 or� representationsby quantum stochasticprocesses. 12 Other
�approachesutilize a more detailedtreat-
ment� of the classical environment.These include simpleadiabatic dynamicswherethe classicalsystemevolveson apotential energy surfacedeterminedfrom a single adiabaticeigenstate,� or Ehrenfestmeanfield modelswherethe classi-cal� evolution is governedby a meanforce determinedfromthe�
instantaneousvalue of the quantumwave function.13,14
These"
descriptionsproducea definiteclassicalevolutionbutdo�
not alwaysgive physicallycorrectresults.If we relax thecontinuity� of thetrajectoryof theclassicalvariables,15 we# areled to considersurface-hoppingalgorithms.16–19 Evolution
equations� for thequantum-classicaldensitymatrix wheretheevolution� operator is expressedin terms of a quantum-classical� brackethavealsobeenstudied2
$0–26 and their solu-
tions�
have been formulated in terms of surface-hoppingtrajectories.� 26–28
In�
this paper we develop the statistical mechanicsofmixedquantum-classicalsystems.We takeasa startingpointthe�
evolutionequationfor the mixed quantum-classicalden-sity� matrix.21,23–26,29This
"equationmaybederivedby partial
W%
igner transformingthe quantumLiouville equationoverthe�
bath degreesof freedomcorrespondingto massivepar-ticles�
andexpandingthe resultingevolutionoperatorto lin-ear� orderin themassratio (m& /
'M(
)) 1/2,* wherem& and M
(are the
characteristic� massesof the quantumsubsystemand bathparticles, respectively.26
$Theresultingevolutionequationcan
be+
recastasan integralequationin which classicaltrajectorysegments� are interspersedwith environment-inducedquan-tum�
transitions and corresponding bath momentumchanges.� 27
$The"
canonicalequilibrium densitymatrix for quantum-classical� systemsis constructedto be stationaryunder thequantum-classical� evolution. Its form is derived and com-pared with its full quantumanalog.A linear responsederiva-tion�
is carriedout to determinetheresponsefunctionandtheformsof theequilibriumtime correlationfunctionsappearingin quantum-classicalsystems.Mixed quantum-classicaldy-namics� and the associatedcorrelationfunctionspresentdif-ferences
from their full quantumanalogs:Identitiesamongquantum� correlation functions hold only approximatelyinthe�
quantum-classicallimit andpropertiessuchastime trans-lation�
invariancearealsoonly approximatelyvalid.The"
paperis organizedasfollows: SectionII presentstheformal structureof mixed quantum-classicaldynamicsandcontrasts� it with that of full quantummechanics.In Sec.IIIwe# discussthe canonicalequilibrium densitymatrix and inSec.�
IV a linear responsederivationof the responsefunction
JOURNAL,
OF CHEMICAL PHYSICS VOLUME 115, NUMBER 13 1 OCTOBER2001
58050021-9606/2001/115(13)/5805/11/$18.00 © 2001 American Institute of Physics
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is carriedout and a generaldiscussionof the propertiesofmixedquantum-classicalcorrelationfunctionsis given.Con-cluding� remarksare madein Sec.V andAppendixesA–Ccontain� additionaldetails.
II.-
QUANTUM-CLASSICAL DYNAMICS
Consider.
a quantumsystemwhich may be partitionedinto!
two interactingsubsystems,a quantumsubsystemwithparticles of massm& ,/ and a quantumbath with particlesofmassM, (/ M 0 m& )
). In order to describethe distinctive fea-
tures�
of quantum-classicaldynamics,we begin with a briefoverview� of the algebraicstructureof quantumandclassicaldynamics�
in the Wigner representationof the quantumbath.
A. Quantum and classical dynamics
The"
von Neumannevolution equationfor the quantummechanicaldensitymatrix 1ˆ is
243ˆ 5 t6 78
t6 9;: i<=?> H@ ˆ ,/ Aˆ B t6 CED ,/ F 1G
where# H@ ˆ is!
theHamiltonianof thesystem.Its formal solutionis
Hˆ I t6 JLK eM N iLtO Pˆ Q 0R SLT eM U iHtO /V WYXˆ Z 0R [ eM iHtO /V \ ,/ ] 2with# iL
< ˆ _ (`i</' a
)) b
H,/ c the�
quantumLiouville operator.And
alternativeform of the evolution equationmay beobtained� by takingthepartialWignertransformoverthebathdegrees�
of freedom.This partial Wigner transform of thedensity�
matrix is definedby
eˆ W f R,/ P gLhji 2 kmlonLp 3q
Nr
dzes iP t zu /V v R w zx
2 yˆ R z zx2
,/ {3| }
while# the correspondingtransformof an operatorA is givenby+
AW ~ R,/ P �L� dzs
e � iP � zu /V � R � zx2
A R � zx2
. � 4�Both�
the densitymatrix and quantumoperatorsretain theirabstract operatorcharacterin thequantumsubsystemdegreesof� freedombut arenow functionsin the � R,
�P� phase spaceof
the�
quantumbath.To proceedwe usethefact thattheWignertransform�
of a productof operatorsis given by30q
�AB � W � R,/ P �L� AW � R,/ P � eM ��� /2
ViBW � R,/ P � ,/ � 5� �
where# the left andright actingdifferentialoperator� is!
thenegativeof the Poissonbracketoperator,
��� �P R ¡ ¢ R £ P ,/ ¤ 6¥ ¦
and the arrowsindicatethe directionsin which the gradientoperators� act.Using this resultandtaking thepartialWignertransform�
of Eq. § 1 we# find
©4ªˆ W « R,/ P,/ t6 ¬
t6 ®;¯ i<°�± HWeM ²´³ /2
Vi µˆ W ¶ t6 ·L¸º¹ˆ W » t6 ¼ eM ½´¾ /2
ViHW ¿
À;Á i<Â�à H@ ÄÆÅÈLj W É t6 ÊL˺̈ W Í t6 Î H@ ÏÆÐÒÑ
Ó;Ô iL< ˆ
W Õˆ W Ö t6 ×Ø;ÙjÚ HW ,/ Ûˆ W Ü t6 ÝEÝ Q . Þ 7ß àIn�
theseequationswe havedefinedthe right (H@ áãâ
))
and left(`H@ äãå
))
actingoperators,
Hæãçéè HW ê R,/ P ë eM ì´í /2V
i,/ î8ï ð
Hñãòéó eM ô´õ /2V
iHW ö R,/ P ÷where# the partially Wigner transformedHamiltonianHW is
H@ ˆ
W ø R� ,/ Pù úLû Pù 2$
2ü
M( ý pþ ˆ 2
$2ü
m& ÿ VW � q�ˆ ,/ R� � . � 9� �
Here pþ ˆ and q�ˆ are the momentumand position operators,respectively� , of the quantumsubsystemand VW(
`q�ˆ ,/ R� )
)is the
partially Wigner transformedtotal potentialenergy operator,which# is the sumof the quantumsubsystem,quantumbath,and subsystem-bathpotentialenergies.
The"
secondequalityin Eq. � 7ß � defines�
thequantumLiou-ville� operatoriL
< ˆW in the partial Wigner representationand
the�
associatedLie bracket(H@
W , )/ Q . More generallythe Liebracket+
of two partially Wigner transformedoperatorsis de-fined as
A ˆ
W ,/ B� ˆ W � Q i<��� A ��� B
� ˆW � B
� ˆWA �����
� i<��� AWeM ��� /2
ViBW � BWeM �! /2
ViAW " . # 10$
Here%
the A &�'
and A (�)
operators� aredefinedasin Eq. * 8ï + with#the�
replacementH@ ˆ
W , A ˆ
W .The"
formal solutionof Eq. - 7ß . is!
/ˆ W 0 R� ,/ Pù ,/ t6 132 eM 4 iH576 tO /V 839ˆ W : R� ,/ Pù ,0/ ; eM iH<7= tO /V >? eM @ iLW
A tO Bˆ W C R� ,/ Pù ,0/ D . E 11FAd
similar setof equationsmay be written for the evolu-tion�
of anyquantumoperatorA ˆ . In theWignerrepresentation
these�
equationsand their solutions, respectively, take theform
dAs ˆ
W G t6 Hdts I iL
< ˆWA ˆ
W J t6 K3LNM H@ ˆ W ,/ A ˆ W O t6 PQP Q R 12Sand
A ˆ
W T t6 U3V eM iLWA tO A ˆ W W eM iHXZY tO /V [ A
ˆWeM \ iH]Z^ tO /V _ . ` 13a
bW%
e shall drop the dependenceof quantitieslike A ˆ
W(`R�
,/ Pù ))
on� the bath phasespacecoordinateswhen confusionis un-likely to arise.c
The"
Wigner transformof a productof operatorssatisfiesthe�
associativeproductrule,
5806 J. Chem. Phys., Vol. 115, No. 13, 1 October 2001 Nielsen, Kapral, and Ciccotti
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dABC e W fNgQg AWeM h�i /2
ViBW j eM k�l /2
ViCW m
nNo AWeM prq /2V
i s BWeM tru /2V
iCW vQv ,/ w 14xwith# an obvious generalizationto productsof ny operators.�Consider.
a quantumoperatorC z AB which# is theproductoftwo�
operators.Sincethe time evolutionof C maybewrittenas C(
`t6 )) { A
ˆ (`t6 )) B� ˆ (
`t6 )) , its partial Wigner transformis
CW | t6 }3~ A ˆ
W � t6 � eM ��� /2V
iB� ˆ
W � t6 � . � 15�W%
e may also obtain this result by consideringthe actionofthe�
Liouville operatoron the operatorproductin the partialW%
igner representation:
iL< ˆ
WCW � i<��� H@ ˆ WeM �r� /2
Vi � A ˆ WeM �r� /2
ViB� ˆ
W �Q�� i<���Q� AWeM ��� /2
ViBW � eM ��� /2
ViHW �
�N� iL< ˆWAW � eM ��� /2
ViBW � AWeM �¡ /2
Vi ¢ iL< ˆ
WBW £ . ¤ 16¥In writing the last line of this equationwe have usedtheassociative property in Eq. ¦ 14§ . From this result we mayimmediatelycomputetherepeatedactionof iL
< ˆW on� CW and,
using¨ thedefinitionof theexponentialevolutionoperatorasapower series,find Eq. © 15ª by
+identificationof thetwo power
series� expansions.We shall makeuseof this lengthierrouteto�
Eq. « 15¬ in the sequelwherethe analogousdemonstrationfor
mixed quantum-classicalsystemsis not so straightfor-ward.#
The quantummechanicalLie bracket,eitherin its origi-nal� form as (i
</'
)) ®
A ˆ ,/ B� ˆ ¯ or� in its partially Wigner trans-
formed
form (A ˆ
W ,/ B� ˆ W))
Q ,/ satisfiesthe Jacobiidentity,°AW ,/ ± BW ,/ CW ² Q ³ Q ´Nµ CW ,/ ¶ AW ,/ BW · Q ¸ Q
¹NºBW ,/ » CW ,/ AW ¼ Q ½ Q ¾ 0.
R ¿17À
W%
e may remark on several limiting situationsof thisgeneralÁ formulation of quantumdynamics.If the quantumbath+
is absentand the systemcomprisesonly quantumsub-system� degreesof freedom,we simply havethe usualquan-tum�
dynamical description in terms of the von Neumannequation� Â 1Ã . If one considersthe quantumbath dynamicsalone without a quantumsubsystem,one has the ordinaryW%
igner representationof quantummechanicsand all par-tially�
Wigner transformedoperatorsbecomesimple phasespace� functions:AW(
`R,/ P)
) ÄAW(
`R,/ P)
). Theclassicallimit of
the�
quantumbathdynamics,which consistsin keepingonlyterms�
of order Å 0Æ
in!
the evolution operator, is obtainedbythe�
following truncationof thepowerseriesexpressionof theexponential� operator:exp(ÇÉÈ /2
'i<)) Ê
1 ËÍÌÏÎ /2'
i<. In this limit
the�
bracket(H@
W , )/ Q reduces� to the PoissonbracketÐ H@ W ,/ Ñand the Wigner representationof the quantum Liouvilleequation� becomesthe classicalLiouville equation, ÒÔÓ C /
' Õt6ÖØ×ÚÙ H@ W,/ Û C ÜÞÝØß iL
<C à C(
`t6 )) , whosesolution may be written
asá
C â R� ,/ Pù ,/ t6 ã3ä eM å iLCæ tO ç
C è R� ,/ Pù ,0/ éê eM ë 1/2H
ìWA í tO î
C ï R,/ P,0/ ð eM 1/2ñ Hì
WA tO . ò 18ó
The Poissonbracketis a Lie bracketandsatisfiesthe Jacobiidentity. Of course,productsof classicalphasespacefunc-tions�
satisfy the associativeproperty. Consequently, bothquantum� andclassicaldynamicshavea Lie algebraicstruc-ture�
and productsof quantumoperatorsor classicalphasespace� functionssatisfyan associativeproductrule.
B. Quantum-classical dynamics
The"
formulation of quantum dynamics in the partialWô
igner representationallows the limit of a mixed quantum-classical� systemto betakeneasily. In suchquantum-classicaldynamics,�
the full quantumdynamicsof the subsystemistaken�
into accountwhile the bath, in isolation, evolvesac-cording� to the classicalequationsof motion. This limit istaken�
by replacingH@ õ÷ö
and H@ øÞù
by+
their expansionsto firstorder� in ú :
H@ ûÞüþý ÿ � ��� H
@ ˆW 1 �
���2i< ,/
�19
H��� �������� 1 ����2i< HW .
The"
full systemevolution,which includestheinteractionbetween+
the quantum subsystemand classical bath, isthen�
given by the mixed quantum-classicalLiouvilleequation:� 2
�0–26
���ˆ W � R,/ P,/ t6 ��
t6 "! i<#%$ H@ ˆ W ,/ &ˆ W ' t6 (*),+ 1
2ü -/. H@ ˆ W ,/ 0ˆ W 1 t6 243
57698ˆ W : t6 ; ,/ H@ ˆ W <>=?"@BA H@ ˆ W ,/ Cˆ W D t6 EFEHG"I i
< J ˆ Kˆ W L t6 M . N 20ü O
The last equalitiesin Eq. P 20Q define�
the mixed quantum-classical� Liouville operatorR ˆ ,/ and the bracketwhich takesthe�
form23,24
SA ˆ
W ,/ B� ˆ W THU i<VXWZY/[H\ B
� ˆW ] B
� ˆW ^`_Hacb
d i<e A
ˆW 1 f
g�h2ü
i< B� ˆ
W i B� ˆ
W 1 jkml2ü
i< A ˆ
W
n i<oXp AW ,/ BW q,r 1
2s`t
AW ,/ BW u�v7w BW ,/ AW x>y ,/ z 21{
where| }/~H� is definedas ����� in Eq. � 19� with| HW � AW . Thebracket�
reducesto thequantumLie bracket(i� �
)� � 1 � A� ˆ W ,� B� ˆ W �
when| the classicalbath is absentand to the classicalLiebracket� �
Poisson�
bracket��� AW ,� BW � when| the quantumsub-system� is absent.
Using�
this notation, the evolution equationsfor �ˆ W(�t� )�
and� an operatorA� ˆ
W are� given, respectively, by���
ˆ W � t� ��t� �¡ B¢ HW ,� £ˆ W ¤ t� ¥F¥ ¦ 22§
and�
5807J.¨
Chem. Phys., Vol. 115, No. 13, 1 October 2001 Statistical mechanics of quantum-classical systems
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dA© ˆ
W ª t� «dt© ¬B HW ,� AW ® t� ¯F¯ ,� ° 23±
in²
apparentcompleteanalogywith purequantumandclassi-cal³ dynamics.However, a numberof importantdifferencesexist´ which we now examine.
Considerµ
the product of three operatorsin the mixedquantum-classical¶ limit. From Eq. · 14 we| have
¹ABC º W » AW 1 ¼
½m¾2i� BW 1 ¿
ÀmÁ2i� CW
 A� ˆ
W 1 ÃÄ�Å2Æ
i� B
Ç ˆW 1 È
ÉmÊ2Æ
i� CW
ËÍÌ 2
4ÎÏÎFÎ
AW Ð BW ÑÓÒ CW ÔÕBÖ AW ×ÙØ BW Ú CW ÛÏÛFÛ ,� Ü 24Ý
where| the last term is Þ (ß à 2)
�. Thus,the associativeproduct
rule is no longerexactbut is valid only to terms á (ß â 2�)�. This
hasimportantimplicationsfor thedynamics.In particular, inthisã
limit, considertheactionof themixedquantum-classicalLiouville operator on the product of two operators,CWä A� ˆ
W(1ß åçæmè
/2é
i�)�BÇ ˆ
W :
i� ê ˆ CW ë i
�ì í�î�ï A
� ˆW 1 ð
ñmò2Æ
i� BÇ ˆ
W
ó i�ô A
� ˆW 1 õ
öm÷2Æ
i� BÇ ˆ
W ø�ùûúüBý i� þ ˆ AW ÿ 1 �
���2i� BW
�A� ˆ
W 1 ����2Æ
i� � i� ˆ B
Ç ˆW ��� ������ . � 25
Æ �Thus, while Eq. � 16� is exact, the correspondingquantum-classical³ equationis valid only to terms � (
ß �)�. From this
result� it follows that
CW � t� ��� e� i ˆ t! CW "$# e� i % ˆ t! A� ˆ W & 1 '(*)2Æ
i� + e� i , ˆ t! BÇ ˆ W -�.�/�02143
5 AW 6 t� 7 1 89*:2i� BW ; t� <>=@?�A�B�C . D 26E
Consequentlyµ
, the evolution of a composite operator inquantum-classical¶ dynamicscannotbedeterminedexactlyintermsã
of the quantum-classicalevolution of its constituentoperators,F but only to terms G (
ß H)�, in contrastboth to quan-
tumã
andclassicaldynamics.This resulthasimplicationsfortheã
computationof time correlationfunctions discussedinSec.I
V.The Jacobi identity involving the quantum-classical
bracket�
is valid only to terms J (ß K
):�
LA� ˆ
W ,� M BÇ ˆ W ,� CW NON�P$Q CW ,� R A� ˆ W ,� BÇ ˆ W SOS�T$U BÇ ˆ W,� V CW ,� A� ˆ W WOWX�Y[Z�\�] ; ^ 27Æ _
thus,ã
the quantum-classicalbracket is not strictly a Liebracket.�
As a consequence,Poisson’s theorem,which statesthatã
thePoissonbracket ` orF thequantumLie bracketa ofF anytwoã
constantsof themotion is alsoa constantof themotion,fails. More generally, from this resultwe concludethatprod-uctsb or powersof theconstantsof themotionareconstantsoftheã
motion only to c (ß d
).�
Thee
formal solutionsof theequationsof motionthatpar-allel� thoseof full quantummechanicsalsorequiresomedis-cussion.³ For example,the formal solutionof Eq. f 23g can³ bewritten| as
A� ˆ
W h t� i�j e� i k ˆ t! AW lnmpo e� i q rts t! /u v AWe� w i x ytz t! /u {�| . } 28~Here�
the operator� specifies� the rule that must be usedtoevaluate´ the exponentialoperatorsin the secondequality inEq. � 28� . AppendixA givesthe detailsof the rulesthat mustbe�
followed in order for the formal solution involving theexponentials´ of the left ����� and� right �2��� operatorsF to beequivalent´ to thatobtainedusingthequantum-classicalLiou-ville� operator.
Given�
this compact formulation of mixed quantum-classical³ dynamicsthat exploits the formal similarity withfull�
quantummechanics,we turn to a descriptionof the sta-tisticalã
mechanicsof such systems.In the next sectionweconsider³ the determinationof the equilibrium densitymatrixfor a mixed quantum-classicalsystemand then turn in thefollowing�
sectionto a moregeneralstudyof thepropertiesofequilibrium´ time correlationfunctions.
III. EQUILIBRIUM DENSITY MATRIX
Thee
quantummechanicalequilibrium canonicaldensitymatrix� hasthe familiar form
�ˆ e�Q � Z� � 1e� ��� H,� � 29
Æ �where| Z
�is²
thepartitionfunction,Z� �
Te
r exp(��� H� ˆ ).�
Its partialW�
igner transformis given by
�ˆ WeQ � R,� P �¡ dz
©e iP ¢ z£ /u ¤ R ¥ z¦
2 §ˆ e�Q R ¨ z¦2
. © 30ª «
W�
e denotethecorrespondingcanonicalequilibriumden-sity� matrix in the quantum-classicallimit by ¬ˆ We(
ßR,� P)
�which| is definedto betheapproximationto ˆ We
Q (ßR®
,� P¯ )�
that isstationary� underquantum-classicaldynamics:
i� ° ˆ ±ˆ We ² i
�³µ´�¶2·¹¸»ºˆ We ¼¾½ˆ We ¿ À¹Á»Â>à 0.Ä Å
31ª Æ
The solution of Eq. Ç 31ª È
can³ be found in the followingway:| we first write Ɉ We as� a powerseriesin Ê$Ë orF in themassratio� (mÌ /
éMÍ
)� 1/2 if
²scaledvariablesareusedÎ
ψ We Ð ÑnÒ Ó 0ÔÕ×Ö
nÒ Øˆ We
ÙnÒ Ú . Û 32
ª ÜSubstitutingÝ
this expressionin Eq. Þ 31ª ß
and� grouping bypowersà of á ,� we obtainthe following recursionrelations:fornâ ã 0:
Äi� ä
HW ,� åˆ We
æ0Ô çéèëê
0Ä ì
33ª í
5808 J. Chem. Phys., Vol. 115, No. 13, 1 October 2001 Nielsen, Kapral, and Ciccotti
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and� for nâ î 0,Ä
i� ï
H� ˆ
W ,� ðˆ We
ñnÒ ò 1 óõô¹ö 1
2÷ ø H� ˆ W ,� ùˆ We
únÒ ûõüþý 1
2÷ ÿ��ˆ We
�nÒ � ,� H� ˆ W
�. � 34
ª �An�
analogousset of recursionrelationsmay be writtenfor�
the partial Wigner transform of the full quantumme-chanical³ canonicalequilibrium densitymatrix. Theserecur-sion� relationsaregivenin AppendixB whereit is shownthat�ˆ We
Q (ßR,� P)
�and ˆ We(
ßR,� P)
�are identical to (
ß �)�. We shall
exploit´ this featurebelow wherethe solutionsof the mixedquantum-classical¶ recursionrelationsarepresented.
It is convenientto analyzethe structureof the recursionrelationsandobtaintheir solutionsin anadiabaticbasis.Theadiabatic� statesaredefinedto be theeigenstatesof thequan-tumã
subsystemwith fixed classicalcoordinates,
h�ˆ
W R� ����� ;R� ���
E� ���
R� �����
;R� �
,� � 35ª �
where|
h�ˆ
W R� !#" P$ ˆ 2%
2Æ
mÌ & VW ' q(ˆ ,� R� ) . * 36ª +
Teaking matrix elementsof Eqs. , 33
ª -and� . 34
ª /,� respec-
tivelyã
, we find,
iE� 0103254
We
60Ô 798:83;=<
0,Ä >
37ª ?
iE� @1@3A5B
We
CnÒ D 1E�F1F3GIHKJ iL
� L1LNMPOWe
QnÒ R9S:S3TIUWVXYX�Z
J[ \1\3]
, ^Y^�_5` We
anÒ b=cYc�d .e
38ª f
This setof equationsis equivalentto gihYh�j i� kml1l3n , oporq5s WetYt�u=v 0Ä
with| wWexYx�y written| asa powerseriesin z . In theseequations,
usingb the definitionsin Ref. 26, we havethe classicalLiou-ville� operator,
iL� {:{3|I} P
MÍ ~~ R
� � 1
2Æ � F� W��� F
�W�3�P� ��
P$ ,� � 39
ª �where| F
�W���W����� ;R
� ���VW(
ßq(ˆ ,� R� )/
� �R� ���
;R� �
is²
the Hellmann–Feynmanforce for state � ,� the energy differenceE �1�3� (ß R)
�� E � (ß R)� �
E N¡ (ß R)�, and the term responsiblefor nonadia-
batic�
transitions,
J[ ¢1¢3£
, ¤Y¤�¥I¦K§ P
MÍ d
© ¨ª©1 « 1
2Æ S¬ :® ¯¯ P
$ °²±3³µ´�¶· P
$M
d© ¸N¹µº�»* 1 ¼ 1
2S¬ ½3¾9¿rÀ* ÁÁ P Â²ÃªÄ . Å 40Æ
InÇ
this equationthe nonadiabaticcouplingmatrix elementis
d© È1ÈNÉ=ÊÌË�Í
;R ÎÐÏÏ R Ñ�ÒÔÓ ;R Õ ,� Ö 41×while| the quantityS
¬ Ø:Ùis²
definedas
S¬ Ú:ÛÝÜßÞ
FWà:áÝâ FWãåä ã:æ ç P
Md© è:é ê 1
ë E� ì:í
d© î:ï P
$M
d© ð:ñ ò 1
,� ó 42ô õ
and� specifiesthe momentumtransferto andfrom the classi-cal³ subsystemarisingfrom quantumtransitions.
Equation ö 37ª ÷
providesà no informationaboutthe diago-nal elementsø We
(0)ù ú1ú�ûýü
We(0)ù þ
but�
requiresthat the off-diagonal
elements´ ÿWe(0)ù �����
be�
zero.Similarly, Eq.�38ª �
for nâ � 0�
pro-vides� no information about the diagonal elements � We
(1)ù
� �We(1)ù �
but�
relatesthe off-diagonalelements� We(1)ù ����
toã
thediagonal�
elements� We(0)ù �
. For nâ � 1 Eq. � 38ª �
determines�
thediagonal�
elements� We(ùn� )� �
in termsof theoff-diagonalelements
ofF thesameorder, andtheoff-diagonalelements� We(ùn� � 1) �� � in
termsã
of the diagonalandoff-diagonalelementsof ! We(ùn� )� "�"�#
.Thus,providedwe know thediagonalelements$ We
(0)% &
thereã
issufficient� information to determinethe completesolutionof'
We(( ) .Thee
methodusedto solveEq. * 38ª +
for�
the diagonalele-ments� ,
We(%n� )- .
requires� somediscussion.Writing this equationexplicitly´ for the diagonalelementswe have
iL� /10
We
2n� 3547698:<;>=@? 2ACB J[ DD , EFE@GIH We
Jn� KMLFL@NPO ,� Q 43R
where| we haveused S WeTT�UWV X WeY�Z\[ * and] J[ ^�^
, _`_baWc J[ dd
, e@f5g* and]theã
fact thatJ[ h�h
, i`i<j 0�
whena realadiabaticbasisis chosen.Theleft-handsideof Eq. k 43l consists³ of a linearself-adjointdifm
ferential operatoriL� n
acting] on the diagonalelementsoftheã
density matrix, iL� o1p
We(qn� )r sutwv
H�
Wx ,� y W(qn� )r z|{
and,] due to thePoisson}
bracket form of this operator, one can determine~W(qn� )r �
onlyF up to a constantof themotionundertheadiabaticHamiltonian�
H�
W� . To insurethat a solutioncanbe found wemust invoke the theoremof the Fredholmalternativewhichrequiresthat the right-handsideof Eq. � 43� be
�orthogonalto
theã
null-spaceof iL� �
.31�
Thise
null-spaceconsistsof the con-stants� of themotionundertheadiabaticHamiltonianH
�W� —at
least�
any function F�
(ßH�
W� (ßR�
,� P$ )�) of this Hamiltonian.Hence
we� mustverify that the following condition is satisfied:
dR©
dP ��<���b� 2��� J[ �� , �F�@�I� We
�n� �M�`�b�P� F � HW� �1¡ 0.
� ¢44£
W¤
e show in Appendix C that ¥ (ßJ[ ¦¦
, §`§b¨I© We(ªn� )« ¬`¬b
)�
isa no ddfunction of P. This, along with the fact that F(
ßHW® ) i
�s an
even¯ function of P$
since° it is a function of the Hamiltonian,guarantees± the validity of Eq. ² 44
ô ³.
Thus,we may write the formal solutionof Eq. ´ 43µ as¶·
We
¸n¹ ºM»7¼�½
iL� ¾1¿1À 1 ÁÂÄÃ>ÅbÆ 2
Æ Ç�ÈJ[ É�É
, ÊFÊ@ËIÌ We
Ín¹ ÎMÏ`ÏbÐPÑ ,� Ò 45
ô ÓandÔ the formal solutionof Eq. Õ 38
ª Öfor� ×ÙØÚ×ÜÛ
asÔÝ
We
Þnß à 1 á5ââ�ãWä i
�E åå�æ iL
� ç�ç�èIéWe
ênß ëMìì�íWîÚïð`ðbñ
J[ òò�ó
, ôFô@õIö We
÷nß øMù`ùbú .û
46ô ü
Using�
the formal resultsoutlined above,we may con-structý the form of the mixed quantum-classicalcanonicalequilibriumþ densitymatrix. In AppendixB we showthat
ÿWe
�0� �����
Z�
0� � 1e �� H
WA � ,� Z
�0� ����� dR
©dPe ��� H
�WA � ,� � 47
ô �andÔ that � We
(1)� ���
0.�
Then,taking n� � 0�
in Eq. 46! we" obtain,after# somealgebra,
5809J.¨
Chem. Phys., Vol. 115, No. 13, 1 October 2001 Statistical mechanics of quantum-classical systems
Downloaded 25 Sep 2001 to 142.150.225.29. Redistribution subject to AIP license or copyright, see http://ojps.aip.org/jcpo/jcpcr.jsp
$We
%1 &(')'+*�,.- i
� P
Md© /0/2143
We
506 7(8 9
2 : 1 ; e< =?> E@ ACBEDGF
H 1 I e< J�K E@ LNMPO
E� Q0Q2R S 1 TVUXW0W+Y4Z . [ 48
ô \W¤
e may then usetheseresultsin the recursionrelationstoobtainF all higher order terms in the expansion.The higherorderF termsare more difficult to evaluateand, as we shallshow] in the following section,theexplicit solutionsto ^ (
ß _)�
will" sufficesinceall resultswe canobtainarereliableonly tothisã
order.
IV. TIME CORRELATION FUNCTIONS
Teo deriveexpressionsfor transportpropertiesin termsof
equilibrium` time correlationfunctions,onemayconsidertheresponseof a systemto an external force using linear re-sponse] theory or monitor the equilibrium fluctuationsin asystem.] In this sectionwe examinelinearresponsetheoryformixed quantum-classicalsystems.
A. Response function
Standarda
descriptionsof linear responsetheory32b
assume#thatã
a systemwhich is in thermalequilibrium in the distantpastà is subjectedto a time dependentexternal force. Theresponsec of thesystemto this externalforceis determinedbycomputing³ theaveragevalueof somepropertyat time t� usingbtheã
densitymatrix determinedto linearorderin theforce.Weadopt# a similar point of view hereexceptthatwe supposethesystem] follows quantum-classicaldynamicsinsteadof fullquantumd mechanics.
The mixed quantum-classicalsystemis subjectedto atimeã
dependentexternalforce F(ßt� )� which couplesto theob-
servable] AW† e †f is theadjointg and# is appliedfrom thedistant
past.à The partially Wigner transformedHamiltonian of thesystem] in the presenceof the externalforce is
HW h t� iNj HW k AW† F l t� m . n 49o
The evolution equationfor the density matrix is obtainedfrom�
Eq. p 22Æ q
by�
replacingrts)u and# vtw)x by�
Hy z|{
(ßt� )� andH
y }|~(ßt� ),�
respectively, to yield���ˆ W � t� ��
t� ��� i� ���N� 1 � Hy �|��� t� ���ˆ W � t� �N���ˆ W � t� � Hy �|��� t� ����. �¡ i� ¢ ˆ £ i
� ¤ ˆA¥ F ¦ t� §¨§¨©ˆ W ª t� « ,� ¬ 50
®where" H|° (
ßt� )� ±³²t´)µ·¶³¸º¹N»
F(ßt� )� and i
� ¼ ˆA hasa form analogous
toã
i� ½ ˆ with¾ A
� ˆW† replacingc H
� ˆW ,� i
� ¿ ˆA¥ À (
ßA� ˆ
W† ,� ). The formal
solution] of this equationis foundby integratingfrom t� 06 toã
t� ,�Áˆ W  t� ÃNÄ eÅ Æ i Ç ˆ È tÉ Ê tÉ 0Ë Ì(͈ W Î t� 06 Ï
ÐtÉ 0ËtÉdt© Ñ
eÅ Ò i Ó ˆ Ô tÉ Õ tÉ ÖØ× i� Ù ˆ A Úˆ W Û t� Ü�Ý F Þ t� ß�à . á 51 â
Choosingµ ã
ˆ W(ßt� 06 )� to be the equilibrium densitymatrix,äˆ We ,� definedto beinvariantunderquantum-classicaldynam-
ics, i� å ˆ æˆ We ç 0,
èthe first term on the right-handside of Eq.é
51 ê
coincidesë with ìˆ We andí is independentof t� 06 . We can
now assumethat thesystemwith HamiltonianHW is in ther-mal� equilibrium from t� î.ï³ð upb to t� 06 . With this boundarycondition,ë to first order in the externalforce Eq. ñ 51
òyieldsó
ôˆ W õ t� öN÷�øˆ We ù úXûtÉdt© ü
eÅ ý i þ ˆ ÿ tÉ � tÉ ��� i� � ˆ A¥ �ˆ WeF � t� �� . 52
�The nonequilibriumaveragevalue of any operatorBW
over� the densitymatrix ˆ W(ßt� ),� B
�(ßt� )� � Tr
� ���dR©
dP BW �ˆ W(ßt� )�
maybecomputedto determinetheresponseof thesystemtothe�
externalforce.Using Eq. � 52 �
we¾ may write this as
�B�
W � t� ��� �! tÉdt© "
Tr� #
dR©
dP BWeÅ $ i % ˆ & tÉ ' tÉ (*) i+ , ˆ A -ˆ WeF� .
t� /0132 4!5tÉ
dt© 687:9
AW† ,; BW < t� = t� >?@?BA F C t� DE
F G!HtIdt© JLK
BAM N t� O t� PQ F� R t� ST ,; U 53
VwhereW X BW(
ßt� )� Y BW(
ßt� )� Z\[ BW ] . In this equationwe made
use^ of integrationby partsandcyclic permutationsunderthetrace_
to movethe evolutionoperatoronto BW and` i+ a ˆ
A ontobB� ˆ
W(ßt� c t� d )� . Thenusingthedefinitionof i
+ e ˆA as` thequantum-
classicalf bracket and the definition of the average g fh ˆ
W ij Tr k�l dR©
dP f W mˆ We for any operatorfh ˆ
W ,; we arrive at theformn
in the secondline. The prime on the tracedenotesthefactn
that the traceis over the quantumsubsystemstates.Thelast line definestheresponsefunction o BA whichW is givenbyp
BA q tr s�t3u\v:w Ax ˆ W† ,y Bz ˆ W { tr |@|B} . ~ 54
�The�
responsefunction in Eq. � 54 �
wasW derivedby consider-ing a systemfollowing quantum-classicaldynamics,in equi-librium in the past, subject to a time dependentexternalforce.n
This quantum-classicalresponsefunction shouldnowbe�
comparedwith the reductionof the responsefunction fora` fully quantummechanicalsystemto its quantum-classicalform.
The�
quantumexpressionfor the responsefunction is32b
�BAMQ � tr ���3� i
+� Tr � A†,y �ˆ e�Q � B � tr ��� i+� Tr � A†,y B � tr �����ˆ e�Q ,y � 55
�which,W taking the partial Wigner transform of the secondequality� in Eq. � 55
�,y may be written as
�BAMQ � tr �¡3¢ Tr £ dR
©dP
i+¤¦¥ AW
† e§ ¨ª© /2«
iBW ¬ tr ® BW ¯ tr ° e§ ±ª² /2
«iAW
† ³µ´ˆ WeQ
¶3· Tr� ¸
dR©
dPi+¹¦º Ax »½¼ B
z ˆW ¾ tr ¿BÀ B
z ˆW Á tr  Ax ýÄLŵƈ We
Q
Ç3ÈÊÉÌË Ax ˆ W† ,y Bz ˆ W Í tr Î@Î Q Ï . Ð 56
ÑT�o obtain the first equality we have usedthe fact that the
partialÒ Wigner transformof Tr AB Ó Tr Ô�Õ dR©
dP AWBW .W¤
e wish to take the mixed quantum-classicallimit ofthis_
expressionbut this cannotbe doneby a simple expan-
5810 J. Chem. Phys., Vol. 115, No. 13, 1 October 2001 Nielsen, Kapral, and Ciccotti
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sionÖ in × . Mixed quantum-classicaldynamicsis definedbythe_
evolution equation Ø 20Ù whereW the evolution operatorisobtainedb by an expansionto first order in ÚÜÛ orb the massratioÝ Þ ; however, the time-evolveddensitymatrix containsallordersb in ß sinceÖ it involvestheexponentialof theevolutionoperatorb . The sameargumentsapply to operatorsat time trand` the equilibrium densitymatrix.
As�
anansatzonemayreplacethe time dependentopera-tor_
Bz ˆ
W(ßtr )à and the quantumequilibrium densitymatrix ሠWe
Q
by�
their quantum-classicalforms. In addition, we may re-placeÒ thequantumLie bracket( , )Q by
�its quantumclassical
analog,` ( , )Q â (ß
, ) which is equivalentto replacingthe ex-ponentialÒ operatorexp(ã!ä /2
éi+)à
by its expansionto linear or-derå
in æ ,y exp(çéè /2é
i+)à ê
1 ëíìïî /2é
i+. After thesereplacements
the_
responsefunction takesthe form
ðBAM ñ tr ò�ó3ô Tr
� õdR©
dPi+ö¦÷ Ax ˆ W
† ø 1 ùíúüû /2é
i+ ý
Bz ˆ
W þ tr ÿ� BW
�tr ��� 1 ���� /2
éi+
AW† � �ˆ We
����� Ax ˆ W† ,y Bz ˆ W � tr ����� ,y � 57
�whichW is exactly the result in Eq. � 54
�obtainedb by perform-
ing�
a linear responsederivation directly on the mixedquantum-classical� equationsof motion. This entitlesone touse^ the above intuitive correspondencerule to convert aquantum� mechanical correlation function to its mixedquantum-classical� analog.
InÇ
thelinearresponseapproachto dynamicalphenomenathere_
arevarioususefulequivalentwaysto representthe re-sponseÖ function. Moreover, since the responsefunction isessentially� an equilibrium correlationfunction, its computa-tion_
is generallysimplifiedby usingthesymmetrypropertiesofb the equilibrium system.As we shall seein the next sec-tions_
the situation is much less favorable in the quantum-classicalf casesincemanyof therigorousequivalencesestab-lished in quantum or classical responsetheory are onlyapproximately` true in the quantum-classicallimit. The firstand` most important equivalenceis obtained through theKubo�
identity; therefore,we begin our discussionwith thiscase.fB. Kubo transformed correlation functions
In quantummechanics,correlationfunctions often ap-pearÒ in Kubo transformedform. Making useof the quantummechanical� identity,
i+�! A†,y "ˆ e�Q #%$
06&
d© ')(
ˆ e�QA† *,+ i+ -.0/
,y 1 58 2
in the first equality of Eq. 3 55 4
weW may write the responsefunctionn
as
5BAMQ 6 tr 798;:
06<
d© =
Tr A† >,? i+ @A0B
B C tr D Eˆ e�QFHG
06I
d© J
Tr K dR©
dP L A†W M N i
+ OQPSRT
eU VXW /2Y
iBW Z tr [�[ \ˆ WeQ ,y ] 59
^
whereW we have again written the secondline in partiallyW¤
igner transformedform. Using the correspondencerule totake_
thequantum-classicallimit of this expression,we obtain
_BA ` tr a9b;c
06d
d© e
Tr f dR©
dP g AW† h i i
+ jk0lmon
1 p�qr /2é
i+ s
Bz ˆ
W t tr u�u vˆ We . w 60x y
W¤
e shall shownow thatEqs. z 57 {
and` | 60x }
are` not equaland` agreeonly to ~������ . The quantummechanicalidentity�Eq.� �
58 ���
used^ to obtain the Kubo transformedcorrelationfunctionusestheexplicit form for thethermaldensitymatrix
ofb �ˆ e�Q � Z� � 1eU ��� H
� ˆ. In thequantum-classicalcasethestructure
ofb �ˆ We is complicated� seeÖ Sec.III � and` we do not haveaclosedf form expressionfor it. Consequently, it is necessarytoobtainb an expressionfor �ˆ We that
_is analogousto �ˆ e�Q soÖ that
manipulations� parallel to those in the quantumderivationmay� be performed.We shall seethat this is possibleonly toterms_ �
(ß � 2�).à
The unnormalizedequilibrium quantumdensitymatrix,� ˆe�Q ,y satisfiesthe Bloch equation,
��� ˆe�Q���¡ ;¢ H £ ˆ e�Q ¤;¥�¦ ˆ e�QH. § 61
x ¨
T�aking its partial Wigner transformwe may write it in the
form
©�ª ˆWeQ
«�¬®;¯ H°²±�³ ˆ WeQ ´;µ�¶ ˆ
WeQ H·¹¸ ,y º 62
x »
withW the boundarycondition ¼ ˆ WeQ (ß ½¿¾
0)À Á
1.The normalizedformal solution  taking
_into accountthe
boundary�
conditionà is�
Ĉ WeQ ŠZ
� Æ 1 Ç eU È�É HÊÌË 1 Í9Î Z� Ï 1 Ð 1eU ÑÓÒ HÔÖÕØ× . Ù 63
x ÚByÛ
the usual rule the quantum-classicallimit should beobtainedb by the replacementH
Ü ÝQÞàß)á. However, by direct
calculationf one may show that (exp(âäã�åçæ�è )1)à
and(ß1 exp(é¿ê�ëíì�î )
à) agreeonly to first orderin ï .33
bMoreover, to
first orderin ð they_
alsoagreewith ñˆ We whoseW explicit formto_
this orderis givenin Eqs. ò 47ó ô
and` õ 48ó ö
. Thus,to this orderthese_
expressionsmay be usedinterchangeably.The Kubo identity ÷ 58
øin the partialWigner representa-
tion_
is
ùûúˆ We
Q ,y AW† ü
Q ý06þ
dÿ ���
ˆ WeQ eU ��� /2
YiAW
† ��� i+ � �
,y � 64x �
and` its quantum-classicalanalog,which holdsonly approxi-mately� , is
���ˆ We ,y AW
† ���06�
dÿ ���
ˆ We 1 ����2i+ AW
† ��� i+ �! "�#%$'&)( *
+-,/.%0'13254 . 6 65x 7
This�
resultis derivedasfollows: performingtheintegralover8weW obtain
5811J.9
Chem. Phys., Vol. 115, No. 13, 1 October 2001 Statistical mechanics of quantum-classical systems
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i+ :�;/<>=@?
ˆ We 1 AB�C2i+ DFE eU GIH J�K AW
† eU LNMIO P�QSR
T@Uˆ We 1 V
W�X2Y
i+ Ax ˆ
W†
Z>[ Z\ ] 1 ^ 1eU _N`Ia b�cSd 1 e
f�g2Y
i+ hFi eU j H
k lnmAx ˆ
W† eU oNpIq r�sSt
u@vˆ We 1 w
x�y2i+ AW
† z%{'|)} 2 ~ ,y � 66x �
whereW we haveusedoneof the ‘‘equivalent’’ expressionsfor�ˆ We ,y andwe remindthereaderthat the interpretationof � ( )�
is�
given in Appendix A. Next, expandingthe exponentialoperatorb andusingthequantum-classicalassociativeproductrule � valid� to terms � (
� � 2�)à �
weW may showthat
�1eU ����� ���S� 1 �
���2Y
i+ � eU �N�I� �����%���)� 2 ,y ¡ 67
¢ £
1 ¤¥�¦2i+ § eU ¨�©�ª «�¬ 1 �® eU ¯N°I± ²�³�´%µ�¶)· 2 ¸ ,y ¹ 68
¢ º
and` usetheseresultsto manipulateEq. » 66¢ ¼
. We have
i+ ½�¾/¿>À
Z Á 1eU ÂNÃIÄ Å�Æ�ÇFÈ eU ÉIÊ Ë�Ì AW† eU ÍNÎIÏ Ð�ÑSÒ
Ó@Ôˆ We 1 Õ
Ö�×2i+ AW
† Ø%Ù'Ú)Û 2Ü Ý
. Þ 69¢ ß
T�o further simplify the right-handside of this equationwe
use^ the relation
eU à�á�â ã�ä�åFæ eU çIè é�ê AW† eU ëNìIí î�ïSð�ñ AW
† eU òNóIô õ�ö�÷%ø�ù)ú 2Ü û
,y ü 70ý þ
whichW maybeprovedby directexpansionof theexponentialoperators.b ThenusingEq. ÿ 68
¢ �weW have
i+ �������
Z\ � 1A
x ˆW† 1
��2Y
i+ � eU ���� ��� 1 �����ˆ We 1 �
���2Y
i+ Ax ˆ
W†
��� �"! 2 #
$�% AW† 1 &
')(2i+ *ˆ We +�,ˆ We 1 -
.�/2i+ AW
† 0�13254 2 6
7 i+ 8:9�;
ˆ We ,y Ax ˆ W† <�=�> ?"@ 2 A . B 71
ý C
StartingD
with Eq. E 54F G
and` usingEq. H 65¢ I
givesJK
BA L tr M�N�O Tr P dRÿ
dP Q AW† ,y BW R tr STSVUˆ We
WYX Tr� Z
dRÿ
dP []\ˆ We ,y Ax ˆ W† ^ Bz ˆ W _ tr `
aYb0cd
dÿ e
Tr f dRÿ
dP AW† gVh i
+ i�jlkm
1 no�p2i+ B
z ˆW q tr r sˆ We tYu v5wyx . z 72
ý {
The last equalityhasbeenobtainedby substitutingEq. | 65¢ }
and` thenusingcyclic permutationof thetraceandintegrationby�
parts.Following~
Kubo, we maydefinea newcorrelationfunc-tion,_
also in the mixed quantum-classicallimit, by
�Ax ˆ
W ;Bz ˆ
W � tr ���V� 1�0c�
dÿ �
Tr� �
dRÿ
dP Ax ˆ
W† ��� i
+ �)�y��
1 ��)�2Y
i+ B
z ˆW � tr � �ˆ We . � 73
ý �
Using�
this notation, the responsefunction may be writtensimplyÖ as
�BAM � tr �������y� Ax ˆ W ;B
z ˆW tr ¡£¢�¤�¥ ¦"§l¨ . © 74
ª «Equation� ¬
74ª
may� be useful in practicalcalculations.How-ever� , since the equivalencebetweenthe two forms of theresponseÝ function ® Eqs.
� ¯57° ±
and` ² 74ª ³µ´
cannotf be establishedto_
all ordersin ¶ ,y themagnitudeof their numericaldifferencemustbe evaluatedin specificapplicationsin order to deter-mine the applicability of Eq. · 74
ª ¸.
C.¹
Time translation invariance
Forº
both quantumand classicalsystemsin equilibriumthe_
time evolution of an observablegeneratesa stationaryrandomprocess.In particular, ensembleaveragesof observ-ables` areindependentof time andtime correlationfunctionsdo»
not dependon the time origin but only on time differ-ences.� For quantum-classicaldynamicstheensembleaverageofb an observableis independentof time,
Tr� ¼
dRÿ
dP AW ½ tr ¾T¿ˆ We À Tr� Á
dRÿ
dP  eU i à tI AÄ ˆ W ÅVƈ We
Ç Tr È dRÿ
dPAW É eU Ê i Ë tÌ Íˆ We ÎÏ Tr� Ð
dRÿ
dPAW ш We ,y Ò 75ª Ó
whereW we haveusedthe stationarityof Ôˆ We ,y while for thetime_
correlationfunction in Eq. Õ 57° Ö
weW only have×ÙØ
AW ,y BW Ú tr ÛTÛ£Ü�ÝßÞáà AW â�ã£ä ,y BW å tr æYç�èTè£é�ê�ë ì"íyî . ï 76ª ð
Indeed,ñ
for the exactequality to hold oneneeds
AW† ò�ó�ô 1 õ
ö)÷2Y
iø BW ù tr úüû£ý�þ AW
† 1 ÿ���2Y
iø BW
�tr � ���� .
77ª �
A special caseof this is, for any operatorsCW and` DW ,yCW(
�tr )à � 1 (
� ���/2�
iø)à �
D� ˆ
W(�tr )à � (
�CW � 1 � (
� ���/2�
iø)à �
D� ˆ
W)(à
tr ).à Anecessary� andsufficientconditionfor this to be true is
iø � ˆ CW 1 �
���2iø DW
�! iø " ˆ CW # 1 $%�&2Y
iø D
� ˆW ' CW 1 (
)�*2Y
iø + iø , ˆ D
� ˆW - . . 78
ª /
5812 J. Chem. Phys., Vol. 115, No. 13, 1 October 2001 Nielsen, Kapral, and Ciccotti
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However, we haveshownin Eq. 0 251 that2
this is trueonly to3547698. Thus,time translationinvarianceis valid only approxi-
mately: in quantum-classicaldynamics.
V. CONCLUSION
The;
resultsobtainedin this paperprovide the basisforthe2
computationof equilibrium time correlationfunctionsinmany-bodyquantum-classicalsystems.The numericalcom-putationÒ of time correlationfunctionsentailsboth the simu-lation<
of the evolution of dynamicalvariablesor operatorsthat2
enterin thecorrelationfunctionof interestandsamplingover= a convenientweight function (exp(>@? H
A ˆW))à
which ispartÒ of the quantum-classicalcanonicalequilibrium densitymatrix. Algorithms havebeendevelopedfor the simulationof= quantum-classicalevolutionandtheir furtherdevelopmentisB
a topic of continuingresearch.Samplingmethodsfor thecalculationC of quantum-classicaltime correlationsrequiread-ditional»
considerations.Typically, in simulationsof classicalequilibriumD time correlationfunctionsthe ensembleaverageisB
replacedby a time averageandthe informationneededtosampleE from the equilibrium distribution is obtainedfrom along moleculardynamicstrajectory. The validity of suchaprocedureÒ hingeson the assumedergodicity andstationarityof= the systemandreplacesdirect samplingfrom the equilib-rium distributionusingMonte Carlo methodsby a time av-erage.D This ensembleaveragemethodhasbeenusedocca-sionallyE but sinceit is not necessaryand is algorithmicallymore complex, requiring both Monte Carlo and moleculardynamics»
programs,its practicalimportancehasbeenminor.Forº
quantum-classicalsystemsneitherthe assumptionof er-godicityF nor stationaritycanbemadeandsamplingfrom theequilibriumD distribution or anothersuitableweight functionmustbe carriedout to evaluatethe correlationfunctions.
The;
analysispresentedin this papergivesall of the in-formationG
neededto computeequilibrium time correlationsin the quantum-classicallimit in a consistentfashion and,thus,2
providesa useful way to treat a large classof many-bodyH
systemswherethe environmentaldegreesof freedomhaveI
a classicalcharacter.
ACKNOWLEDGMENTSJ
This work was supportedin part by a grant from theNaturalK
Sciencesand Engineering ResearchCouncil ofCanada.L
Acknowledgmentis madeto the donorsof The Pe-troleum2
ResearchFund,administeredby theACS, for partialsupportE of this research.Oneof theauthorsM S.N.
N OwouldP like
to2
acknowledgea Walter C. SumnerMemorial Fellowship.
APPENDIX A
The;
meaningof the formal solutionin thesecondequal-ity in Eq. Q 28R willP beestablishedhereby comparingthetwoforms in this equation
AW S tr TVUXWZY eU i [ \^] t_ /Y ` AWeU a i b c^d t_ /Y ef ,y g A1handi
AW j tr kVl eU i m ˆ t_AW . n A2o
The first few terms p thought2
of asa powerseriesexpan-sionE in it
q/� r�s
are,i from Eq. t A2u ,yeU i v ˆ t_ AW w AW x it
qy{z}|�~�� AW � AW � �����V� tr 2
2� 2� �}�����9�}��� AW
�X������� AÄ ˆ W � �����V�!�}���� AÄ ˆ
W ¡£¢ ¤�¥�¦ AÄ ˆ
W § ¨�©9ª�«�¬®
¯ itq 3°
6¢ ± 3
° ²�³�´�µ9¶�·�¸9¹�º�» AW ¼X½ ¾�¿9À�Á�Â�à AW Ä Å�Æ®Ç
ÈXÉ�Ê�Ë�ÌÍÌ�Î}Ï�Ð AW Ñ£Ò Ó�Ô�ÕÖØ×}Ù�Ú�Û AW Ü Ý�Þ9ß�à�á�âã!ä}å�æ�ç9è�é�ê AW ë£ì í�î�ï!ð}ñ�ò�óõô
AW ö ÷�ø®ùÍù£ú�û�üý!þ}ÿ�� � AÄ ˆ
W���������� ��
AÄ ˆ
W � ����������������� ,� � A3 !
and,i from Eq. " A1 #
,�$
e% i & '�( t_ /) * AÄ ˆ
We% + i , -/. t_ /) 0
1 AÄ ˆ
W 2 itq35476�8�9�: A
Ä ˆW ; AÄ ˆ
W < =�>�?�@ tA 2�2B C 2 DFE�G H�IJ�K�L A
Ä ˆW
M 2N�O�P AW Q R�S�T AW U V�WX�Y�Z\[�] itq 3°
6¢ ^ 3
° _7`�a�b�cd�e�fg�h�i AW
j 3k l�m�no�p�q
AÄ ˆ
W r s�t�u 3k v�w�x
AÄ ˆ
W y z�{|�}�~� AÄ ˆ
W � �������������\��� . � A4 �
For theseexpressionsto agreewe must make assignmentslike<�7�������
AÄ ˆ
W � ����������� 1
3� ��������� AW �¡ ¢�£¤�¥�¦�§©¨�ª�«�¬® AW ¯ °�±\²�²�³�´�µ¶¸·�¹�º®»
AÄ ˆ
W ¼ ½�¾¿�À�Á�Â� . à A5 Ä
In generalthe term Å ((� Æ�Ç�È
)É jÊAW(
� Ë�Ì�Í)Î kÏ)Î
is composedof ( jÐÑ
kÒ)!/Î
jÐ! kÒ! separatetermseachwith a prefactorof j
Ð! kÒ!/( jÐÓ
kÒ)Î! . Eachof theseseparatetermscorrespondsto a unique
associationi of terms indicating the order in which the ÔÖÕoperators= act.
APPENDIX B
This;
appendix concernsthe relationship betweenthequantum× Øˆ We
Q (�RÙ
,� PÚ )Î
and quantum-classicalÛˆ We(�RÙ
,� PÚ )Î
equi-libriumÜ
densitymatricesin thecanonicalensemble.We beginbyH
derivingtherecursionrelationsfor thequantummechani-calC equilibrium densitymatrix.
The thermaldensitymatrix ݈ WeQ is stationaryunderthe
quantum× dynamicsin Eq. Þ 7ª ß ,�0à á©â
Hã ˆ
W ,� äˆ WeQ å
Q
æ içèêé Hã ˆ Weë ìîí /2
ïi ðˆ We
Q ñ5òˆ WeQ eë óõô /2
ïiHã ˆ
W ö . ÷ B1ø ù
5813J.ú
Chem. Phys., Vol. 115, No. 13, 1 October 2001 Statistical mechanics of quantum-classical systems
Downloaded 25 Sep 2001 to 142.150.225.29. Redistribution subject to AIP license or copyright, see http://ojps.aip.org/jcpo/jcpcr.jsp
If we substitutethe expansion,
ûˆ WeQ üþý
nÿ � 0�
� �ˆ WeQ � nÿ ��� nÿ ,� B2
ø into Eq. � B1� andi groupby powersof weP obtain � using� thefactG
that the PÚ
dependence»
of Hã
isB
of the form PÚ 2/2
�M� �
0à ���
iç ����� 1 � HW ,� �ˆ We
Q � 0� � �
,� ! B3"0à #%$ 0
� &iç '
Hã ˆ
W ,� (ˆ WeQ ) 1 * +-, 1
2. /ˆ We
Q 0 0� 1�2
Hã ˆ
W 3 12. Hã ˆ
W 465ˆ WeQ 7 0
� 8:9,� ; B4
ø <0à =%> 1 ? i
ç @Hã ˆ
W ,� Aˆ WeQ B 2
C D E-F 1
2G H We
Q I 1 J�K Hã ˆ
W L 1
2G Hã ˆ
W M%Nˆ WeQ O 1 P
Q 1
8R
iç S We
Q T 0� U�V
2CHã ˆ
W W 1
8R
iç Hã ˆ
W X 2C Y
ˆ WeQ Z 0
� [,� \ B5
ø ]
0à ^%_ 2 ` i
ç aHW ,� bˆ We
Q c 3d e f-g 1
2 hˆ WeQ i 2
C j�kHW l 1
2HW m%nˆ We
Q o 2C p
q 1
8R
iç r We
Q s 1 t�u 2CHã ˆ
W v 1
8R
iç Hã ˆ
W w 2C x
ˆ WeQ y 1 z|{ 1
48} ~ We
Q � 0� ���
3dHã ˆ
W
� 1
48HW � 3
d �ˆ We
Q � 0� �
,� � B6�andi soon. Theseresultsshouldbecomparedwith themixedquantum-classical× recursionrelationsgiven in Eqs. � 33
k �andi�
34k �
.NoticeK
that the first two recursionrelationsareidenticalinB
the quantum-classicalandfully quantummechanicalsys-tems2 �
seeE Eqs. � 33k �
andi � 34k �
for n� � 0,à �
B3� ,� and � B4��� .Hence,we cancalculatethe first two termsfor the quantummechanical� system� inB the partially Wigner transformedrep-resentation� � andi the results will also be valid for thequantum-classical× system.
In quantummechanicswe have for the unnormalizedcanonicalC equilibrium densitymatrix, � ˆ We
Q
� ˆWeQ �¡ eë ¢¤£ H
k ˆ ¥W
¦ 1 §6¨ Hã ˆ
W ©ª 2
C2G Hã ˆ
Weë «¬ /2ï
iHã ˆ
W ® . ¯ B7ø °
This powerseriesin ± mustbeconvertedinto a powerserieswithP respectto ² . Extractingthe first two termsin this newpower³ seriesgives
´ ˆWeQ µ eë ¶¸· H
k ˆW¹ º¼»
2iç
½Hã ˆ
W¾P
¿nÿ À 0
�Á ÂÄÃ6ÅÇÆ
nÿ È 2Én� Ê 2 Ë !
̼ÍjÎ Ï
0�
nÿ Ðn� Ñ 2
GjÐ Ò
Hã ˆ
Wnÿ Ó j
Î Ô HWÕRÙ H
ã ˆWjÎ ÖØ×ÚÙÜÛ
2C Ý
,� Þ B8ø ß
afteri isolatingthezerothandfirst ordertermsandprovingbyinductionB
to first order in à that2
áHnÿ â 2 ã
W
ä1stå æ|çéè
2iç ê H
ã ˆWë
P
ìjí î
0�
nÿ ïn� ð 2 j
ñ òHW
nÿ ó jí ô Hã ˆ
WõR
HWjí
. ö B9÷The operatorsHW andi ø HW /
� ùR do»
not commuteandso theorder= mustbe preservedasshown.
It is possibleto show that in the adiabaticbasisrepre-sentationE ú properlyû normalizedü these
2are the resultsquoted
inB
Eqs. ý 47} þ
andi ÿ 48} �
. We haveestablishedthe equivalencebetweenH
the secondterm on the right-handsideof Eq. � B8ø �
andi Eq. � 48� byH
a direct calculationwhich showsthat thematrix representationof this term in Eq. � B8� is the sameasthe2
Taylor expansionof Eq. � 48} �
inB
powersof .
APPENDIX C
Here we establish that (�J� � �
, ������� We(�nÿ )� �����
)�
isa no ddfunctionG
of PÚ
. Using the definitions in Sec. III, this isequivalent� to the condition that � ((
� �(�P/�M )�
d� ���! *" 1
2. E# $ $!%
d� & &!'* (
� (/� )
PÚ
))� *
We(�nÿ )� +�+!,
)�
be an odd function of PÚ
or= ,choosingC to work with a real adiabaticbasisso that d
� - -!.is
real,� this simplifies to the conditionsthat PÚ /
(� 0
We(�nÿ )� 1 132
)�
and4/� 5
PÚ 6
(� 7
We(�nÿ )� 8 8!9
)�
be odd functionsof PÚ
. The effect of multi-plicationû by P or= differentiation with respect to P is to
changeC the parity of the factor : (� ;
We(�nÿ )� < <3=
)�, if indeed this
factor has a definite parity; thus, we must show that>(� ?
We(�nÿ )� @ @!A
)�
is an evenfunctionof PÚ
. For technicalreasonsit
willP alsobeusefulto showthat B (� C
We(�nÿ )� D�D!E
)�
is an oddfunctionof= P.
WF
e usean inductive proof. The statementsare true for
nG H 1. From Eq. I 48J weP seethat K We(1)� L�LNM
0à
andthat O We(1)� P�P!Q
is pure imaginaryandodd in P for RTSURWV . AssumingXZY\[We
]nÿ ^`_�_!acb even� function of P dfe ,� gWh ,� nG ,� i C1
j klnm\o
We
pnÿ q`r r3sct odd= function of P
Ú ufv,� wWx ,� nG ,� y C2
j zweP show that theseconditionsare true for nG { 1. From Eq.|46} }
weP have
~����We
�nÿ � 1 �`� �3�c��� 1
E ���!� � PÚM
��R�����
We
�nÿ �`� �!�c�
� 1
2G � F� ��� F
� �!�c ¢¡¡ PÚ £�¤\¥ We
¦nÿ §`¨ ¨3©cª
«¬ ®�¯ d° ± ±�² 1
2E ³�³�´¶µµ P · P
M ¸�¹�º We
»nÿ ¼¾½�¿�À!ÁcÂ
Ãd° Ä3Å�ÆÈÇ 1
2G E# É!ÊÌË�ͶÎÎ P
Ú Ï PÚM� Ð�Ñ�Ò We
Ónÿ Ô¾Õ Õ�ÖØ× .
ÙC3Ú Û
Eachof the termson theright-handsideis evenwith respect
to2
P soE Ü (Ý Þ
We(ßnÿ à 1) á�á!â )ã is even in P. The analysis ofä
(Ý å
We(ßnÿ æ 1) ç ç!è )ã is similar andwill be omitted.Thus,the state-
ment is true for né ê 1 completingthe inductiveproof.
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C. Tully, in Modernì
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A-
specificexampleis enoughto demonstratethe inequivalenceof thesetwo
tquantities.The secondorder in � terms
tfor a two-level quantum
subsystemin the adiabaticbasishavebeenexplicitly calculated� analyti-cally� andshownto be different.
5815J.�
Chem. Phys., Vol. 115, No. 13, 1 October 2001 Statistical mechanics of quantum-classical systems
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