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Page1of15PhysicalChemistryChemicalPhysics
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“Inverted”COmoleculesonNaCl(100):Aquantum
mechanicalstudy
ShreyaSinhaaandPeterSaalfranka
0DQXVFULSW
Somewhatsurprisingly,inverted(“O-down”)COadsorbatesonNaCl(100)wererecentlyobserved
experimentallyafterinfraredvibrationalexcitation(Lauetal.,Science2020,367,175-178).Here
wecharacterizethesespeciesusingperiodicdensityfunctionaltheoryandaquantummechanical
-
sion,forlow(1/8and1/4monolayers(ML))andhigh(1ML)
appliedtoestimatethermalratesfor“C-down”to“O-down”isomerizationandthereverseprocess.
Forthe1/4MLp(11)structure,two-dimensionalandthree-dimensionalpotentialenergysurfaces
andcorrespondinganharmonicvibrationaleigenstatesobtainedfromthetime-independentnuclear$FFHSWHG
Schrö(i)rathercoverage-independentCOinversionenergies
()andcorrespondingclassicalactivationenergiesfor“C-down”
to“O-down”isomerization();(ii)thermalisomerizationrates
at22Kwhicharevanishinglysmallforthe“C-down”to“O-down”isomerizationbutnon-negligible
forthebackreaction;(iii)several“accidentallydegenerate”pairsofeigenstateswellbelowthebarrier,
eachpairdescribing“C-down”and“O-down”localizedstates.
3K\VLFV
,atcoverage=1,theP/Uphaseis
,a
Adsorbedmoleculesonalkalihalidesurfaceshavepreviously
1,2p(11)P/U!p(21)T/Aphasetransitionoccurs9,where
servedasmodelstostudyphysisorption,two-dimensional
phasetransitions3,vibrationalrelaxation4,laserinduceddes-“T/A”standsfor“tilted/antiparallel”.Thisstructurewasalso
:30:,COonNaClconflrmedbytheorytobethemoststablemonolayerphaseof
CO:NaCl(100)atverylowtemperatures7,10,,using
isaprototypicalmodelinsurfacescience,whichcontinuesto
attractattention,notonlyforbenchmarkingquantumchemicallargeelementarycellsand/orclustermodels,alsosomenew,&KHPLFDO
methods7,butalsoforpracticalreasons,oneexamplebeinglessstableconflgurationswithirregular,spiralandantiparallel
theuseofvibrationalsignaturesofCOassensitiveprobesforCOarrangementswerepredictedbyDFT,forexampleT/I
unravellingprocessesinheterogeneouscatalysis8.(“tilted/irregular”)andT/S(“tilted/spiral”)phases,atvarious
,Meyerandtheircoworkers12,
Aplethoraofstudieshavefocusedonunderstandingtheforcoverages=1and1/4alsotiltedminimawerefound,often
interactionofadsorbedCOmoleculeswithNaCl(100)–seemorestablethantheP/Uones,byperiodicDFTcalculationswith
,employingtwo-layerslabmodels.
&KHPLVWU\
ofCOonNaCl(100)generallyyieldsa“C-down”conflguration
whereintheCOmoleculepreferentiallyadsorbsinanuprightCOatNaCl(100)alsodisplaysfascinatingeffectswhen
,,mid-infraredlaserex-
“parallel/upright”(P/U),canbefoundforallcoveragesuptocitationofCOmoleculesonNaClresultsin“vibrational
onemonolayer(ML),.,oneCOperNa+inthesurfacelayer,energypooling”,whereCOmoleculesefflcientlytransfervi-
whenusingperiodicmodelsandDensityFunctionalTheoryinbrationalenergyamongthemselves,accordingtoasequence
CO(v=n)+CO(v=m)!CO(v=n+1)+CO(v=m1)13,
theGeneralizedGradientApproximation(DFT-GGA)including3K\VLFDO
thiswayaccumulatingmultiplequantainoneandthesame
,thislongknownenergypoolingwas
are-investigatedbyWodtkeandcoworkers14viainfrared(IR)
TheoreticalChemistry,InstituteofChemistry,UniversityofPotsdam,Karl-Liebknecht-
-25,14476Potsdam,Germany;Tel:+49(0)331-977-5232;E-mail:emission,showingsignalsfromvibrationallevelsashighas
peter.******@uni-=27.
+PVSOBM/BNF
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1–15|1:.
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AnotherinterestingflndingofWodtkeandcoworkers15,isfor“Cdown”!“Odown”reactionsandthebackreaction,at
the“flipping”ofadsorbedCOmoleculesonNaCl(100),wereportglobaltwo-and
infraredlaserexcitationatatemperatureof7K15,fromathree-dimensionalpotentialenergysurfacesforisomerization,
“C-down”toan“O-down”
-
onaNaCl(100)slabalreadyinanearliertheoreticalworkcallycorrected,reactionandactivationenergies,butshowalso
,thelifetimeofthe“O-down”someinterestingfeatures:Ofparticularmentionaresub-barrier
isomerwasfoundtobeshortforasingleCOmonolayeronvibrational“doublets”ofbotheduct(“C-down”)andproduct
theNaCl(100)surfaceexposedtovacuum,.,itisomerized(“O-down”)character,whichcouldplayaroleduringisomeriza-
backto“C-down”in<,addingmore(100)tionbeyondpathwaysprovidedbytheexcitationoftheC-Obond.
COoverlayersonthetopofthemonolayerresultedinthe
stabilizationofthe“O-down”
22Kconvertedthisisomertothenormal“C-down”
Further,experimentalfrequencyshiftsof+-(100)
withrespecttothegasphase13C18Omoleculewereobservedindifferentsubsectionsdealingwithenergiesandharmonic
forthe“C-down”and“O-down”isomers,,frequenciesofstationarypoints,MinimumEnergyPaths(MEPs),
the“O-down”C-Ofrequencyisred-“C-down”,bythermalisomerizationrates,2Dand3DPESsand,flnally,
about17cm1,
.
Theresultswerealsointerpretedasshowingthe“C-down”
conflgurationforthevibrationallyunexcitedmolecule(v=0)2MethodsandModels
beingmorestablethanatv=1,andthereversebeingtruefor$FFHSWHG

“O-down”.Thisconjecturewascorroboratedbythementioned
theoreticalworkofGuo,Meyerandcoworkers12,whoobserveaWeuseperiodicDFTcalculationstodescribetheelectronic
reversedenergyorderofthetwoisomersiftheC-OvibrationisstructureofCOadsorbedonNaCl(100).WeadoptedDFTin
excited,withtheexcitationmodelledbyanelongatedC-,usingthePerdewBeckeErnzerhoffunctionalPBE16
TheaccompanyingchangeindipolemomentsandresultingwithGrimme’sD2dispersioncorrection17asimplemented
frequencyshifts,werearguedtoaidintheflippingoftheCOintheViennaAbinitioSimulationPackage18–21(VASP).The
123K\VLFV
adsorbatesfrom“C-down”to“O-down”.GuoandcoworkersioncoresweredescribedbytheProjectorAugmentedWave
alsopresentedsix-dimensionalPotentialEnergySurfaces(PES)(PAW)method22,andanenergycutoffof700eVwasapplied
fortwocoverages,1and1/4ML,forp(11)andp(22)
,trainedfromforG-centeredk-
AbInitioMolecularDynamics(AIMD),quasi-
:30:,alsohybrid,functionals,andevenhighlyaccurate,
Despitethisprogress,
ispossible,,wherePBEwas
toexploretheisomerizationofCOatCO:NaCl(100).Itisthe&KHPLFDO
goalofthecurrentpapertoshedmorelightonthisreaction,bycombinedwithothertypesofdispersioncorrections.
emphasizingthequantumnatureofthevibrationswhichhasnot
(100)surfacewasmodelledusingthreelayerslabsand
inversionofCOhasalreadybeendemonstratedexperimentallydifferentsupercellsfordifferentcoveragesaslistedinTable1.
(notablytheT/Aone-monolayerphase),butlow-coverageP/UAsshowninAppendixA,,thethree-layerslabandchosen
phaseswithcoverages1/8and1/4aswellinordertoexcludek-pointgridsweresufflcienttoconvergeadsorptionenergiesof
possibleeffectsofexplicitCO-COinteractionsonisomerizationCOonNaCl(100)andenergydifferencesbetween“C-down”and
andvibrations,,“O-down”isomerstowithin
&KHPLVWU\
independentoftheworkreportedinRef.,weflndandcharac-
terizethe“O-down”isomer,forcoverage=1/4(inap(22)cell)
fortheP/Uphase,andforcoverage=1MLfortheT/Aphase1/4withonemoleculepercelleach,andcoverage1withtwo
(p(21)),byperiodicDFT-GGAcalculationswithdispersionmoleculespercell,respectively.
,westudyalowcoveragelimit,the
coverage=1/8P/Uphase,-FirsttheslabmodelswithoutCOwereoptimized,withdetails
siderapossibledouble-,COwasaddedandthegeom-
3K\VLFDO
inthep(21)T/A,coverage=,withallthelayersoftheNaClslabexceptthetop
stationarypoints(educt,“Cdown”,product,“Odown”,,stable“C-down”and
state),wealsopresentminimumenergypathsfromreactantsmeta-stable“O-down”conflgurationsofCOwerefoundwhen
andproducts,againnecessarilyinpartsimilartowhathasbeenusinginitial“C-down”or“O-down”conflgurationsontopofa
+ion,“C-down”conflgurations
2|1–15+PVSOBM/BNF
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Table1Supercellsandk-
ofCOonthree-layerNaCl(100)
numberofNa+sitesavailablefortheadsorptionofCOmoleculesontheWealsocomputedglobal,reduced-dimensionalpotentialen-
surfacelayer,ofwhichthereareeight