Cold Chemistry : molecular scattering and reactivity near absolute zero

692 Pages·2018·170.88 MB·English

by  Olivier Dulieu

ColdChemistry
MolecularScatteringandReactivityNearAbsoluteZero
1
0
0
P
F
0-
0
8
6
2
6
2
8
7
1
8
7
9
9/
3
0
1
0.
1
oi:
d
g |
or
c.
s
s.r
b
u
p
p://
htt
n
o
7
1
0
2
er
b
m
e
c
e
D
5
. n 0
o
d
e
h
s
bli
u
P
View Online
TheoreticalandComputationalChemistrySeries
Editor-in-chief:
JonathanHirst,UniversityofNottingham,Nottingham,UK
1
0
0
P
F Advisoryboard:
0-
80 Joan-EmmaShea,UniversityofCalifornia,SantaBarbara,USA
6
62 DongqingWei,ShanghaiJiaoTongUniversity,China
2
8
7
1
8 TitlesinthisSeries:
7
9
9/ 1: Knowledge-basedExpertSystemsinChemistry:NotCountingon
3
0
1 Computers
0.
oi:1 2: Non-CovalentInteractions:TheoryandExperiment
d 3: Single-IonSolvation:ExperimentalandTheoreticalApproachesto
org | ElusiveThermodynamicQuantities
sc. 4: ComputationalNanoscience
bs.r 5: ComputationalQuantumChemistry:MolecularStructureandProperties
u
p
p:// inSilico
htt 6: ReactionRateConstantComputations:TheoriesandApplications
on 7: TheoryofMolecularCollisions
7
1 8: InSilicoMedicinalChemistry:ComputationalMethodstoSupportDrug
0
2
er Design
b
m 9: SimulatingEnzymeReactivity:ComputationalMethodsinEnzyme
e
ec Catalysis
D
5 10: ComputationalBiophysicsofMembraneProteins
. on 0 11: ColdChemistry:MolecularScatteringandReactivityNearAbsoluteZero
d
e
h
s
bli
u
P
Howtoobtainfuturetitlesonpublication:
Astandingorderplanisavailableforthisseries.Astandingorderwillbring
deliveryofeachnewvolumeimmediatelyonpublication.
Forfurtherinformationpleasecontact:
BookSalesDepartment,RoyalSocietyofChemistry,ThomasGrahamHouse,
SciencePark,MiltonRoad,Cambridge,CB40WF,UK
Telephone:(cid:67)44(0)1223420066,Fax:(cid:67)44(0)1223420247
Email:[email protected]
Visitourwebsiteatwww.rsc.org/books
View Online
Cold Chemistry
Molecular Scattering and
1 Reactivity Near Absolute Zero
0
0
P
F
0-
0
8
6
2
6
2
8
7
1
78 Editedby
9
9/
3
0
1 OlivierDulieu
0.
1
oi: CNRS,Universit´eParis-Sud,ENSParis-Saclay,Universit´eParis-Saclay
d
g | Email:[email protected]
or
c.
s.rs and
b
u
p
p:// AndreasOsterwalder
n htt InstituteofChemicalSciencesandEngineering,EcolePolytechniqueF´ed´eralede
7 o Lausanne(EPFL),Switzerland
1
0 Email:andreas.osterwalder@epfl.ch
2
er
b
m
e
c
e
D
5
. n 0
o
d
e
h
s
bli
u
P
View Online
1
0
0
P
F
0-
0
8
6
2
6
2
8
7
1
8
97 TheoreticalandComputationalChemistrySeriesNo.11
9/
3
0
1 PrintISBN:978-1-78262-597-1
0.
1 PDFISBN:978-1-78262-680-0
oi:
d EPUBISBN:978-1-78801-355-0
g | ISSN:2041-3181
or
c.
s
s.r AcataloguerecordforthisbookisavailablefromtheBritishLibrary
b
u
p
p:// (cid:13)C TheRoyalSocietyofChemistry2018
htt
on Allrightsreserved
7
1
0
2 Apartfromfairdealingforthepurposesofresearchfornon-commercialpurposesorfor
ber privatestudy,criticismorreview,aspermittedundertheCopyright,DesignsandPatents
m
e Act1988andtheCopyrightandRelatedRightsRegulations2003,thispublicationmay
c
De notbereproduced,storedortransmitted,inanyformorbyanymeans,withouttheprior
. n 05 permissioninwritingofTheRoyalSocietyofChemistryorthecopyrightowner,orinthe
o caseofreproductioninaccordancewiththetermsoflicencesissuedbytheCopyright
d
e LicensingAgencyintheUK,orinaccordancewiththetermsofthelicencesissuedbythe
h
s
bli appropriateReproductionRightsOrganizationoutsidetheUK.Enquiriesconcerning
Pu reproductionoutsidethetermsstatedhereshouldbesenttoTheRoyalSocietyof
Chemistryattheaddressprintedonthispage.
Whilstthismaterialhasbeenproducedwithallduecare,TheRoyalSocietyofChemistry
cannotbeheldresponsibleorliableforitsaccuracyandcompleteness,norforany
consequencesarisingfromanyerrorsortheuseoftheinformationcontainedinthis
publication.Thepublicationofadvertisementsdoesnotconstituteanyendorsementby
TheRoyalSocietyofChemistryorAuthorsofanyproductsadvertised.Theviewsand
opinionsadvancedbycontributorsdonotnecessarilyreflectthoseofTheRoyalSocietyof
Chemistrywhichshallnotbeliableforanyresultinglossordamagearisingasaresultof
relianceuponthismaterial.
TheRoyalSocietyofChemistryisacharity,registeredinEnglandandWales,Number
207890,andacompanyincorporatedinEnglandbyRoyalCharter(Registered
No.RC000524),registeredoffice:BurlingtonHouse,Piccadilly,LondonW1J0BA,UK,
Telephone:(cid:67)44(0)20743786556.
Forfurtherinformationseeourwebsiteatwww.rsc.org
PrintedintheUnitedKingdombyCPIGroup(UK)Ltd,Croydon,CR04YY,UK
5
0
0
P
F
0-
0
8 Foreword
6
2
6
2
8
7
1
8
7
9
9/
3
0
1
0.
1 Thisbook,publishedbytheRoyalChemicalSociety,presentsadvancesthat
oi:
d are elucidating the dynamics of cold molecular collisions. In the past two
org | decades, new experimental and conceptual tools have opened up a broad
sc. frontier field. Its range is now extreme: from temperatures below 100 K in
bs.r upper parts of the Earth’s atmosphere, to 10 K in interstellar gas clouds,
u
p
p:// to below the cosmic background at 2.7 K, and vastly lower to millikelvin,
htt microkelvin,andnanokelvinregimesinterrestriallaboratories.Themission
on ofthebookisevangelical:toprovideacollectionoftutorialsonkeyproper-
7
1 ties of cold chemistry, designed to introduce the new field and its tools to
0
2
er students at the advanced undergraduate level and beyond, by augmenting
b
m curriculartopicsaswellaspreparingforresearchprojects.
e
ec The editors, Olivier Dulieu and Andreas Osterwalder, have recruited
D
5 authors who are adept in exposition and leaders in research. Their tutori-
. n 0 als deliver, with intrepid enterprise and exploratory zest, many ideas and
o
ed techniques developed in pursuing cold chemistry. Readers are invited to
h
s
bli an intriguing smorgasbord. It features major aspects of collisions at low
u
P temperatures:
• quantum phenomena that emerge when de Broglie wavelengths
become comparable to or longer than the size or the separation of
molecules;
• long-rangemolecularinteractionsbecomedominantbecausecollision
partnersapproachslowly;
• impactparametersshrink,therebyquenchingcentrifugalbarriers,and
resonanceandtunnelingbecomeprominentinreactions;
• applyingexternalelectricormagneticfieldscanstronglyinfluenceboth
intermolecularandintramolecularinteractions.
TheoreticalandComputationalChemistrySeriesNo.11
ColdChemistry:MolecularScatteringandReactivityNearAbsoluteZero
EditedbyOlivierDulieuandAndreasOsterwalder
(cid:13)C TheRoyalSocietyofChemistry2018
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
v
View Online
vi Foreword
Alsoincludedare:
• casestudiesofprototypicalreactions,includingreactionsofionswith
neutralmolecules,whichareexceptionallyfacileandprominentincold
5
0 interstellarclouds;
0
FP • experiments with large superfluid helium nanodroplets as hosts for
0-
0 coldreactions;
8
26 • aremarkabletheorythatenablesarotatingvagabondmoleculetomas-
6
2
8 queradeasasimplequasiatomwithinacrowd,beitaultracoldgasor
7
1
8 heliumnanodroplet;
7
9/9 • innovativemethodstoslowthecollisionspeedofmoleculesandtotrap
3
10 them,particularlyinopticallatticesmadebyinterferinglaserfields;
10. • meanstoformultracolddiatomicmoleculesbyassociationofultracold
doi: atoms,therebyreachingthenanokelvinregime.
g |
or
c. Anespeciallylucidtutorial,placedasthelastchapter,aptlyservesasthe
s
bs.r dessert area (at least for my taste): Christiane Koch describes a variety of
u
http://p echleegmanictawl raeyascttoionextpolofiatvocrohoenreenotr aqnuoatnhteurmprsoudpuecrtpoosuittcioonmes.taDteessptiotesitneehrera-
n entchallengestocoherentcontrolofcoldcollisions,afew“...experiments
o
17 havedemonstratedthebasicfeasibility... thefullpotentialremainsyettobe
0
er 2 explored.”Hercommentappliestomuchoftheadventurouscoldmolecule
mb frontier.
e
c This book, along with its unique tutorial emphasis, joins kindred collec-
e
D
5 tionsofinvitedresearchpapersoncoldmolecules.Theseappearintwosem-
. n 0 inal books: Low Temperatures and Cold Molecules, edited by I. W. M. Smith
o
ed (Imperial College Press, London, 2008) and Cold Molecules: Theory, Experi-
h
blis ment, Applications, edited by R. V. Krems, W. C. Stwalley, and B. Friedrich
Pu (CRC Press, Boca Raton, FL, 2009), as well as in many websites and now
almostyearlyinspecialissuesofjournals;themostrecentoftheseisSpecial
Issue:ColdMolecules, edited by J. M. Doyle, B. Friedrich, and E. Narevicius,
Chem.Phys.Chem.17,3580–3825,2016.
Beyondtheinvitedpapers,manymorearepublishedorpresentedincon-
ferences; the total annual output is now well above 100, contributed from
about40labsspreadover17countries.Forinstance,therecentChem.Phys.
Chem. special issue contains 28 papers produced by 115 authors, from 10
countries.Ofthosepapers,15reportexperiments,13presenttheory;abouta
thirdofeachcategoryaredevotedtodesignsortestsofproposedtechniques.
ColdChemistryanditssiblingstestifytothevigorandappealofthefield.
For me, surveying the evolution of research on cold molecular collisions
brings on intense nostalgia. Today, “warm” chemical dynamics is going
strong.Yet60yearsago,Iandotherearnestyoungsterswereadvisedbydis-
tinguished seniors that to pursue chemistry at the level of single collisions
was“onthelunaticfringe.”Wewerebuoyedbyasenseofhistoricalimper-
ative; it pertains too now for cold molecules. Grizzled veterans take pride
in passing on molecular beam and laser techniques and collision theory.
View Online
Foreword vii
Wealsoadmirethetenacityandcreativityofsuccessorswhoenhancesuch
toolsandproduceunanticipatednewtoolsandnewperspectives.Thosewill
oftenimpactotherareasconsideredalreadycivilized.
It’sajoytoapplaudColdChemistry.
5
0
0 DudleyHerschbach
P
F
0- HarvardUniversity
0
8
6
2
6
2
8
7
1
8
7
9
9/
3
0
1
0.
1
oi:
d
g |
or
c.
s
s.r
b
u
p
p://
htt
n
o
7
1
0
2
er
b
m
e
c
e
D
5
. n 0
o
d
e
h
s
bli
u
P
View Online
5
0
0
P
F
0-
0
8
6
2
6
2
8
7
1
8
7
9
9/
3
0
1
0.
1
oi:
d
g |
or
c.
s
s.r
b
u
p
p://
htt
n
o
7
1
0
2
er
b
m
e
c
e
D
5
. n 0
o
d
e
h
s
bli
u
P
9
0
0
P
F
0-
0
8 Preface
6
2
6
2
8
7
1
8
7
9
9/
3
0
1
0.
oi:1 Research on molecular collision dynamics at low energies, and with con-
g | d trol of nearly all degrees of freedom, has made tremendous progress in
or recent years, opening many new avenues to study the most fundamental
c.
s.rs aspectsofmolecularinteractionsingeneralandofchemicalreactiondynam-
ub ics in particular. Generally, cold chemistry refers to dynamical processes
p
p:// between atoms and molecules, taking place in the gas phase at tempera-
htt turesor—moreprecisely—energiesthatarelowenoughforthedynamicsto
n
o bedominatedbythelong-rangeinteractionbetweenparticles,andbyquan-
7
01 tumeffectslikeresonancesortunnelingwhichalsoimpliesalownumberof
2
er angularmomentumpartialwavesthatcontributetothecollision.Aquanti-
b
m tative assessment of the relevant temperature ranges is difficult and would
e
c
e requiresystem-specificdefinitions,sincetheinteractionpotentialschange,
D
5 andthedynamicsaremass-dependent.Nevertheless,aroughclassification
. on 0 can be made by defining 1 kelvin as the limit to the so-called cold regime
d
he whiletemperaturesbelow1microkelvinareconsideredultracold.
s
bli Withthepresentbookweintendtoprovidereaderswiththefoundations
u
P neededtounderstandthisexcitingresearchfield,byintroducingandreview-
ing both the theoretical and experimental aspects of research in cold and
ultracold molecular collisions. The book features 13 chapters written by
world-leading scientists in the field. We deliberately avoided arranging the
chapters into traditional blocks of “theory” and “experiment”. Instead, we
propose to the reader an itinerary exploring various ambitious experimen-
taltechniquesthathavebeendevelopedinthepastyearsspecificallyforthe
studyofcoldchemistry,intermingledwiththedescriptionofthenecessary
basic,andstilldeveloping,theoreticalconcepts.
Weopenwithapresentationoftheveryfirstexperimentalapproachthat
enabled the study of chemical kinetics at temperatures in the 10 K range,
TheoreticalandComputationalChemistrySeriesNo.11
ColdChemistry:MolecularScatteringandReactivityNearAbsoluteZero
EditedbyOlivierDulieuandAndreasOsterwalder
(cid:13)C TheRoyalSocietyofChemistry2018
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
ix
View Online
x Preface
namely the CRESU technique (the name is the French acronym for “reac-
tionkineticsinuniformsupersonicflow”)thatmakesuseofuniformflows
in molecular beams and of the low relative molecular velocities therein.
Fournier,LePicard,andSims(Chapter1)demonstratetheimmenseinterest
9
0 ofthisapproachtoinvestigatethebehaviorofgas-phasechemicalreactions
0
P
F at temperatures as low as 7 K, both for fundamental interest and for their
0-
0 relevance in atmospheric and interstellar chemistry. Molecular beams are
8
6
2 alsoatthebasisofthemerged-andlow-anglecrossed-beamtechniquespre-
6
2
8 sented by Naulin and Bergeat (Chapter 3), nowadays allowing dynamical
7
1
8 studiesatenergiesaslowas10mK.Thedevelopmentofaccuratemodelsfor
7
9
9/ coldelasticandinelasticscatteringisahighlychallengingtaskonitsown,
3
10 as discussed by Kłos and Lique (Chapter 2) who present the relevant the-
0.
1 oretical and numerical approaches that start from the Born–Oppenheimer
doi: approximation.
g | TheaccuratedescriptionofvanderWaalsinteractionsbetweengas-phase
or
c. particles is critical for an understanding of their dynamics. This is partic-
s
bs.r ularly true at low temperatures where these attractive interactions begin to
u
http://p dbyomLeinpaetrestahnedcoDlulilsiieoun(dCyhnaapmteicrs4.)Thwihsomdoetsivcaritbesetihnedtheteaoirlythweorgkepnreersaelnttheed-
n ory of long-range interactions between atoms and molecules, applied here
o
17 to ultracold collisions well below 1 K. Hapka and Z˙uchowski (Chapter 5)
0
er 2 demonstratehowtousethetheoryofintermolecularinteractionsinthecon-
mb textofcoldandultracoldchemistry,inparticularhowtoapplytheformalism
e
c of symmetry-adapted perturbation theory (SAPT), which provides partition-
e
D
5 ing of the interaction energy into physically meaningful components such
. n 0 aselectrostatic,dispersion,inductionandexchangeinteractions.Tscherbul
o
ed (Chapter 6) discusses the modification of long-range interactions induced
h
blis by the presence of external electromagnetic fields. This chapter gives an
Pu overviewofthemechanismsforcontrollingmolecularcollisions,bothelas-
ticandinelastic.ItrevealsthecentralroleofFeshbachresonances,whichis
oneofthetopicsatthefocusofChapter7byCôtéinthelastofthesefourthe-
oreticalchapters.Startingfromthebasicconceptsofresonancesinquantum
systems,possibilitiesofmodifyingandcontrollingthebehaviorofultracold
atomicandmoleculargasesbyusingresonancesareinvestigated.
Ahighlyinterestingenvironmentforthestudyofcoldmoleculardynamics
isprovidedbyheliumnanodroplets,i.e.,ensemblesofthousandsofhelium
atomswithatemperaturearound0.4K.Tanyag,Jones,Bernando,O’Connell,
Verma, and Vilesov (Chapter 8) give a detailed introduction to the thermo-
dynamics of such systems, as well as to experimental techniques for their
productionandinvestigation.LemeshkoandSchmidt(Chapter9)presenta
verynewapproachtothedescriptionofimpuritiesinheliumnanodroplets
byintroducinganewquasiparticle,the“angulon,”thatcanalsobeusedto
describethedynamicsofparticlesembeddedinthedroplet.
Chapters 10 and 11 report on two main current experimental pillars of
ultracold chemistry. Cold ion–molecule chemistry is introduced by Zhang
and Willitsch (Chapter 10) who describe theoretical concepts required