Time-dependent density functional theory applied to clusters and molecules in contact with an environment

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Time-dependent density functional theory applied to

clusters and molecules in contact with an environment

Phuong Mai Dinh

To cite this version:

Phuong Mai Dinh. Time-dependent density functional theory applied to clusters and molecules in

contact with an environment. Atomic and Molecular Clusters [physics.atm-clus]. Université Paul

Sabatier - Toulouse III, 2009. �tel-00981941�

Toulouse 3

THÈSE pour l'obtentionde l'

Habilitation à Diriger des Re her hes

Spé ialité : Physique Théorique

présentéepar

Phuong Mai DINH

Time-dependent

Density Fun tional Theory

applied to Mole ules and Clusters

in onta t with an Environment

Théorie de la fon tionnelle de la densité dépendante du temps

appliquée à des molé ules et des agrégats

en onta t ave un environnement

soutenuele 7dé embre2009 à Toulouse

devant laCommission d'examen :

Monsieur Julio A.Alonso Rapporteur

Monsieur XavierBlase Rapporteur

Monsieur Jean-PaulCro ombette Président dujury

Monsieur Karl-Heinz Meiwes-Broer Examinateur

Abstra t

Wepresentre enttheoreti alandmethodologi alexplorations onthedynami sofsodium

lustersinthe framework ofTime-Dependent DensityFun tionalTheory(TDDFT), oupled

non-adiabati ally to Mole ular-Dynami s (MD). In parti ular, a hierar hi al approa h, in

the spirit of Quantum-Me hani al/Mole ular-Me ha ni al methods, has been developed for

the des ription of metal lusters in intera tion with a dynami allypolarizable substrate, as

raregases or MgO. Numerousexamplesof appli ation of thisapproa h(Na lusters inor on

Ar substrate, Na lusters deposited on MgO; opti al response, dynami al deposition, laser

irradiation, ...) arereviewed.

We also briey dis uss omplementing resear h a tivities. Formal developments on the

Self-Intera tion Corre tion issueinDFTand TDDFT aredis ussed ina word. We have

fur-thermoreextendedour TDDFT-MDtheoryto the aseoforgani (C,N,O,Hmade)systems

and a few examples of investigated dynami al pro esses are presented. Re ent al ulations

of photoele tron angular distributions of free metal lusters are reported aswell. We nally

sket h withsome perspe tivesfor theyears to ome.

Résumé

Nous présentons des développements théoriques et méthodologiques sur la dynamique

d'agrégatsdesodiumdansle adredelathéoriedelafon tionnelledeladensitédépendantedu

temps(TDDFT), oupléenonadiabatiquementàdeladynamiquemolé ulaire(MD).En

parti- ulier,uneappro hehiérar hique,s'inspirantdesméthodes

Mé anique-Quantique/Mé anique-Molé ulaire,aétéélaboréeandedé riredesagrégatsmétalliquesau onta tave unsubstrat

de polarisabilité dynamique. Denombreux exemples d'appli ations de ette appro he

(agré-gatsde Na dansousurun substratd'Ar,agrégats deNa déposéssur MgO;réponseoptique,

dynamiquede dépt, irradiationlaser, ...) sont passésen revue.

Nous exposons aussi brièvement quelques a tivités de re her he omplémentaires. Des

développements formels sur le problème de la orre tion de l'auto-intera tion en DFT et en

TDDFT sont rapidement dis utés. De plus, nous avons étendu notre théorie de

TDDFT-MD au asde systèmes organiques ( omposés de C, N,O, H)etquelques exemplesd'études

de pro essus dynamiques sont présentés. De ré ents al uls de distributions angulaires de

FirstIhave been honoredthatProf.Karl-Heinz Meiwes-Broer hasa epteda memberofmy

habilitation jury, andI greatly thank him for that. When we ollaborated for thewriting of

a Review of Modern Physi s, I already appre iated and beneted from his deep knowledge

and understanding in luster physi s, espe iallywhen they aredepositedon or embedded in

anenvironment.

I also thank Prof. Julio A. Alonso to have a epted to be one of the referees of my

habilitationthesis. He isoneoftheworldwideexpertsofDFTand TDDFT,and Ihopethat

myhabilitation thesiswill be an opportunityfor future ollaborations.

My friendship with M. Xavier Blase goes ba k more than (already!) ten years ago; I

deeplythank him to have been one of the referees of mythesis, and thus to have taken the

heavyresponsibilityforjudgingmys ienti a tivities. Hisexpertiseonabinitiosimulations,

espe iallyonnanotubesandsemi ondu tors,allowstoappre iatemyworkinadierentlight.

I thank Prof. Paul-Antoine Hervieux who has been hosen as the third referee of my

thesis. Sometheoreti al toolsthathe hasdevelopped during thepastyears arevery lose,if

not identi al, to those usedin Toulouse. He is probablyone of the physi ists inFran e who

possessesthe deepestexpertiseon thetheorywe developinToulouse. Iregretted hisabsen e

at myhabilitation defense.

M. Jean-Paul Cro ombette has a long experien e in ab initio simulations of defe ts in

insulators, and inoxydes inparti ular. The link withthehierar hi al method we developed

inToulouse isthus obvious. I thank himto have assumed the(heavy!) role of thepresident

ofmyjury.

IthankSylvainVidalto havea epted thehard taskto be myvery rstPh.D.student. I

alsothankMatthiasBaer,GaspardBousquet,BernhardFaber,FrankFehrer,JérémieMessud,

Uguette Ndongmouo, Zhiping Wang, and Philipp Wopperer for their work inour group and

for theirfriendship.

Ithank olleaguesintheLaboratory forTheoreti al Physi s inToulouse,for their

friend-ship, their ollaboration in tea hing, and their ompany during lun htime. I would like to

thank in parti ular Olivier Giraud, former lassmate at the É ole polyte hnique and at the

D.E.A. for Theoreti al Physi s. I will regret our many dis ussions on physi s or on other

subje ts (thatI willnot detail forsake ofpriva y!).

Of ourse,I expressmysin eregratitude toProf. Eri Suraud,who believedinme, when

Iwas nishingmyPh.D. and whenI arrived inToulouse in2002. The numerous dis ussions

Ihave with Prof.Suraud,ons ienti topi saswell ason hildren,musi ,tea hing, ooking,

well whatever the subje t, are always interesting and very instru tive. I really take a great

pleasureto work withhim andour now longstanding ollaboration is very promising for the

years to ome. He has also onstantly inmind mys ienti arrier and relentlessly suggests

meproposalsinthatsense. I thusdeeply thankhim for allthis.

Inevitably joined withProf. Suraud omes Prof. Paul-Gerhard Reinhard, whoI heartily

inToulouse are always fruitful, while they probably represent for him a unique opportunity

to pra tise hislove for trains and subways. His availabilityon emails hasalso been onstant

all overthe years, allowing me to re eive emails from him on a De . 23th. I hope his lose

retirement will not prevent him to keep an eye on physi s and to allowfurther ollaboration

withour group.

Lastbutnotleast,IwouldliketowarmlythankmyhusbandPhilippe,whohas onstantly

givenmehissupportformywork. Hishelpandhisuniqueunderstandinghas ertainlyplayed

adeterminant role inmy arrier.

FinallyI dedi atethis thesisto myfather whore ently passed away. Without doubt, his

love for s ien e, history, philosophy and ulture has strongly surrounded my hildhood. If

I hose to enter upon an a ademi arrier, this is probablydue thanks to his inuen e. He

I Bibliographi al note 1

I.1 Curri ulumVitae . . . 2

I.2 S ienti produ tion . . . 4

I.3 Supervisionand tea hing a tivities . . . 8

II Thesis 11

II.1 Dynami sof lusters in onta t withan environment . . . 12

II.2 Complementary resear h a tivities . . . 13

Bibliographi al note

Contents

I.1 Curri ulumVitae . . . 2

I.2 S ienti produ tion . . . 4

I.2.1 Listofpubli ations . . . 4

I.2.2 Oral ommuni ationsleadingto onferen epro eedings . . . 6

I.2.3 Oral ommuni ationsnotleadingto onferen epro eedings . . . 6

I.2.4 Seminarsin laboratories . . . 7

I.3 Supervisionand tea hing a tivities . . . 8

I.1 Curri ulum Vitae

Phuong Mai DINH, spouseSÈVE Laboratory for Theori al Physi sof Toulouse

Born8 June 1974 inParis (Fran e) IRSAMC, UniversityPaul Sabatier,and CNRS

Fren h 118 Routede Narbonne Bât. 3R1B4

Married,2 hildren F-31062Toulouse edex

Telephone : +33(0)5 6155 74 57

Fax: +33 (0)561 5560 65

email: dinhirsam .ups-tlse.fr

Edu ation and Degrees

•

1999-2002Ph.D.inTheoreti alPhysi s,É olepolyte hnique(June2002,Palaiseau,Fran e)

•

1998-1999 Graduatestudies inTheoreti al Physi s,

É oleNormale Supérieure ofParis /É ole polyte hnique

•

1995-1998 É ole polyte hnique inPalaiseau, Fran e

S ientifi Carrier

•

Sin e 2003 : Assistant Professor, Univ. PaulSabatier, Toulouse 3,Fran e

•

2002-2003 : Post-do toral fellow at the Laboratory for Theoreti al Physi s, Univ. Paul Sabatier, Toulouse, Fran e

S ientifi A tivities

•

Sin e 2002 : Mi ros opi theories for the dynami s of nitefermioni systems

 Time-dependentdensityfun tionaltheory(TDDFT)non-adiabati ally oupledwith

mole -ular dynami s (MD) for the des ription of the dynami s of strongly irradiated alkaline

lusters

 Hierar hi alapproa hofmetal lustersin onta twithaninertsubstrate(raregas,MgO)

withexpli it dynami alpolarizability

 Extensionof our TDDFT-MDto smallorgani mole ules underirradiation

 Formaldevelopments ofDFTand TDDFTon theself-intera tion orre tion

•

1998  2003 : Colle tive ee ts inultrarelativisti heavy ion ollisions

 Theories of signatures of the quark-gluon plasma reation in ultrarelativisti heavy ion

ollisions

 Phenomenologi al model of the

J/ψ

suppression in ultrarelativisti heavy ion ollisions observedat the CERN fa ility

 Elaborationof ananalysismethod,basedona umulant expansion,for theextra tionof

Publi ations and onferen es

•

31 publi ationsininternational peerreviewed journals, in luding2 reviewarti les

•

17 pro eedingsand arti lesinbooks

•

12 parti ipations ininternational onferen es, in luding 6 oninvitation

•

9 seminarsinlaboratories, in luding7 oninvitation

S ientifi administration

•

Memberof the Physi s DeptCommittee at theUniversity PaulSabatier (Toulouse 3)

•

Member of the Re ruitment Committee for Theoreti al Physi s at the University Paul Sabatier (Toulouse 3)

•

Correspondent at the University Paul Sabatier of the European proje t STEPS (Stake-holders Tune European Physi s Studies), held by EUPEN (EUropean Physi s Edu ation

Networks)

•

Formerrepresentative ofnon-permanent fellows at theIRSAMC(Institute forResear h on Complexe Atomi andMole ular Systems)Comittee (2002-2003)

Other responsabilities and a hievements

•

Co-author of O éans et gouttelettes quantiques, P. M. Dinh, J. Navarro, É. Suraud, CNRS Éditions, Paris (2007)

•

Memberoftheorganization ommitteeofthe27theditionoftheinternational onferen eon CondensedMatterTheories (Sep3th8th2002,Toulouse); and o-editorwithM. Belka em

of thepro eedings, Condensed Matter Theories, Vol. 19, Nova S ien e (2005)

Awards

•

Daniel Guinier JeuneCher heur prize of theFren h So ietyof Physi s (SFP),2002 http://sfp.in2p3.fr/Prix/prix.html

I.2 S ienti produ tion

I.2.1 List of publi ations

[1℄ Modeling of the deposition of Na Clusters on MgO(001)

M. Bär, P. M.Dinh ,L. V.Moskaleva,P.-G. Reinhard,N.Rös h, andE. Suraud,

Phys.Rev. B80 (2009)195404

[2℄ Time-dependentGeneralizedSIC-OEPformalismandGeneralizedSIC-Slaterappr

oxima-tion,

J.Messud,P.M. Dinh ,P.-G. Reinhard, andE. Suraud,

Phys.Rev. A80(2009) 04450

[3℄ Signatures from laser-driven non-linear luster dynami s,

Th.Fennel,K.-H. Meiwes-Broer,J.Tiggesbaumker, P.-G. Reinhard,P.M. Dinh ,andE.

Suraud,

a epted inRev. Mod.Phys.(2009),preprint arXiv:0904.2706

[4℄ Generalized Slater andstati polarizabilities

J.Messud,P.M. Dinh ,P.-G. Reinhard, andE. Suraud,

Chem. Phys.Lett. 479 (2009)300

[5℄ Dynami s of lusters and mole ules in onta t withan environment

P.M. Dinh, P.-G. Reinhard,and E. Suraud,

Physi s Reports (2009)inpress, preprint arXiv:0903.1004

[6℄ Mi ros opi studies of atom-water ollisions

Z. P. Wang, P.M. Dinh, P.-G. Reinhard, E. Suraud, G. Bruny, C. Montano, S. Feil,

S.Eden,H. Abdoul-Carime, B.Farizon, M. Farizon,S.Ouaskit, and T.D. Maerk,

Intern. J.MassSpe tr.285(2009) 143

[7℄ Dipoleex itations of Arsubstrate in onta twith Na lusters

P.M. Dinh, F.Fehrer,P.-G. Reinhard,and E. Suraud,

Surf.S i. 603 (2009)400

[8℄ Onthe exa t treatment of Time Dependent Self-Intera tionCorre tion

J.Messud,P.M. Dinh ,P.-G. Reinhard, andE. Suraud,

Annals of Physi s (NY)324 (2008)955

[9℄ Time-Dependent Density-Fun tionalTheory witha Self-Intera tionCorre tion

J.Messud,P.M. Dinh ,P.-G. Reinhard, andE. Suraud,

Phys.Rev. Lett.101 (2008) 096404

[10℄ Deposition dynami s of Na monomers anddimers on an Ar(001) substrate

P.M. Dinh, F.Fehrer,P.-G. Reinhard,and E. Suraud,

Surf.S i. 602 (2008)2699

[11℄ Improved Slater approximation to SIC-OEP

J.Messud,P.M. Dinh ,P.-G. Reinhard, andE. Suraud,

Chem. Phys.Lett. 461 (2008)316

[12℄ Self-intera tion orre tion ina simplemodel

[13℄ Embedded metal luster in strong laser elds

F. Fehrer,P.M. Dinh, P.-G. Reinhard,and E. Suraud,

Comp. Mat.S i. 42(2008) 203

[14℄ Dynami s of luster depositionon Ar surfa e

P.M. Dinh, F.Fehrer,P.-G. Reinhard,and E. Suraud,

Eur. Phys.J. D45 (2007)415

[15℄ Dynami s of metal lusters in rare gas lusters

M. Baer,G. Bousquet,P.M. Dinh ,F.Fehrer, P.-G. Reinhard,and E. Suraud,

Intern. J.Mod.Phys.B21(2007) 2439

[16℄ Size and harge ee ts on the deposition of Na on Ar

P.M. Dinh, F.Fehrer,P.-G. Reinhard,and E. Suraud,

Intern. J.Quant. Chem.107 (2007)2828

[17℄ Stru tural properties andopti al response of Na lusters in Ne, Ar,and Kr matri es

F. Fehrer,P.M. Dinh, P.-G. Reinhard,and E. Suraud,

Phys.Rev. B75(2007)235418

[18℄ Hindered Coulomb explosion of embedded Na lusters  stopping, shape dynami s and

energy transport

F. Fehrer,P.M. Dinh, M. Baer,P.-G. Reinhard,and E. Suraud,

Eur. Phys.J. D45 (2007)447

[19℄ Shape dynami sduring deposit of simple metal lusters on rare gas matri es

P.M. Dinh, F.Fehrer,G. Bousquet,P.-G. Reinhard,and E. Suraud,

Phys.Rev. A76(2007) 043201

[20℄ Pump and probe analysisof metal luster dynami s

K. Andrae, P.M. Dinh ,P.-G. Reinhardand E. Suraud,

Comp. Mat.S i. 35(2006) 169

[21℄ Time resolved ssion in metal lusters

P.M. Dinh, P.-G. Reinhard and E.Suraud,

J. Phys.B38(2005) 1637

[22℄ Analysisof luster dynami s

K.Andrae, M.Belka em,P. M.Dinh ,E. Giglio,M.Ma,A.Pohl,P.-G.ReinhardandE.

Suraud,

Le tureNotesinPhysi s,Formationof orrelations(Nonequilibriumatshorttimes ales)

Springer, Berlin2003.

[23℄ Dire ted andellipti owof hargedpionsandprotonsinPb+Pb ollisionsat40-A-GeV

and 158-A-GeV

C. Altet al.[NA49 Collaboration℄,

Phys.Rev. C68(2003) 034903

[24℄ J/psi suppression in entral Pb Pb ollisions

P.M. Dinh, J.P.Blaizot andJ. Y.Ollitrault,

Nu l. Phys.A 698(2002) 579

[25℄ Ee ts of momentum onservation on the analysisof anisotropi ow

[26℄ Analysisof dire ted owfrom ellipti ow

N.Borghini,P.M. Dinhand J.Y.Ollitrault,

Phys.Rev. C66(2002)014905

[27℄ Flow analysis frommultiparti le azimuthal orrelations

N.Borghini,P.M. Dinhand J.Y.Ollitrault,

Phys.Rev. C64(2001)054901

[28℄ A new method for measuring azimuthal distributionsin nu leus-nu leus ollisions

N.Borghini,P.M. Dinhand J.Y.Ollitrault,

Phys.Rev. C63(2001)054906

[29℄ Transverse energy u tuations and thepattern of J/psi suppression in Pb Pb ollisions

J.P.Blaizot,P.M. Dinhand J.Y.Ollitrault,

Phys.Rev. Lett.85 (2000)4012

[30℄ Are owmeasurements at SPS reliable ?

N.Borghini,P.M. Dinhand J.Y.Ollitrault,

Phys.Rev. C62(2000)034902

[31℄ Ee ts of HBT orrelations on ow measurements

P.M. Dinh, N.Borghiniand J.Y.Ollitrault,

Phys.Lett. B477(2000) 51

[32℄ DFTstudies of ethylene in femtose ond laser pulses,

Z. P.Wang,P.M. Dinh ,P.-G. Reinhard,E. Suraud, and F.S.Zhang,

submitted to Phys. Rev.A (2009)

[33℄ High-order harmoni generation and multi-photon ionization of ethylene in laser,

Z. P.Wang,P.M. Dinh ,P.-G. Reinhard,E. Suraud, and F.S.Zhang,

submitted to THEOCHEM (2009)

[34℄ Angular distributions of ele trons emitted from free and deposited Na

8

lusters M. Bär, P. M.Dinh ,L. V.Moskaleva,P.-G. Reinhard,N.Rös h, andE. Suraud,

submitted to Eur.Phys.J.D

I.2.2 Oral ommuni ations leading to onferen e pro eedings

P1) Metal luster ssion: Adynami al study by a pump-probe analysis

International workshopon O-shell Ee tsinQuantum Transport

Dresden, Germany, May4-16 2003 (invited)

P2) Transverse energy u tuations : The pattern of

J/ψ

suppression in Pb-Pb ollisions 15thInternationalConferen eonUltra-Relativisti Nu leus-Nu leusCollisions(QM2001)

Stony Brook, NY,USA,Jan. 15-202001

I.2.3 Oral ommuni ations not leading to onferen e pro eedings

C1) Dynami s of metal lusters in onta t withan environment : A hierar hi al approa h

C2) Time-dependent density fun tionaltheory in metal lusters

International workshopon Mean FieldDynami sand Beyondfor Nu learRea tions

ENST/CEA Sa lay, Fran e, Jan 23-272006 (invited)

C3) Dynamique de la ssion d'un agrégat : Analyse pompe-sonde

Annualgeneral meeting oftheFren htheoreti ians innu lear physi s

Lyon, Fran e, April1st2003

C4) Collisions d'ions lourds ultrarelativistes : Eets olle tifs

Annualgeneral meeting oftheFren hSo ietyofPhysi s

Paris,Fran e, Feb. 1st2003 (invited)

C5) Dire ted andellipti owfrom multiparti le umulants at160

A

GeV NA49Collaboration Meeting

GSI, Darmstadt, Germany,April8-12 2002 (invited)

C6) Collisions d'ions lourds ultrarelativistes : Le ot elliptique et les orrélations azimutales

7th Meeting ofYoung Resear hers inNu learPhysi s

Aussois,Fran e, De . 10-142001

C7) Colle tiveow analysis : A umulant expansion of multiparti le azimuthal orrelations

NA49Collaboration Meeting

CERN, Genève, Switzerland, O t. 21-252001 (invited)

C8) Collisions d'ions lourds ultrarelativistes : La suppression du

J/ψ

Annualgeneral meeting oftheFren htheoreti ians innu lear physi s

Orsay, Fran e, Mar h22th2001

C9) Plasma dequarks et de gluons : Le ot dans les ollisions d'ions lourds ultrarelativistes

7th Meeting ofYoung Resear hers inNu learPhysi s

Aussois,Fran e, De . 3-82001

C10) Ultrarelativisti heavy ion ollisions: Flowanalysis

12thSummerS hoolinNu learPhysi s

Santa Cruz,CA, USA,July 3-14 2000

I.2.4 Seminars in laboratories

S1) L'argon : un matériau inerte?

Joined seminar ofthe Laboratory for Theoreti al Physi s andtheLaboratory for

Quan-tum Chemistryand Physi s

Toulouse,Fran e, 19juin2008 (invited)

S2) Collisions d'ions lourds ultrarelativistes : Analysedes eets olle tifspar l'étude de

or-rélations azimutalesmultiples

GANIL seminar

Caen, Fran e, June 23th2003 (invited)

S3) Dynamique dela ssiond'un agrégat métallique : Analysepompe-sonde

IRSAMC seminar

Toulouse,Fran e, Mar h14th2003 (invited)

S4) Eets olle tifs dans les ollisions d'ions lourds ultrarelativistes

S5) Collisions d'ions lourds ultrarelativistes : Le ot elliptique et les orrélations azimutales

Ph.D. day,Servi e for Theoreti al Physi s ofCEA/Sa lay

Sa lay,Fran e, Nov. 13th 2001

S6) Charmonium suppression in entral nu leus-nu leus ollisions at SPS andRHIC

GSITheory Seminar

Darmstadt, Germany,May21st 2001 (invited)

S7) Colle tive owanalysis : Multiparti le azimuthal orrelations

Institut fürKernphysik Seminar

Frankfurt, Germany,May 14th2001 (invited)

S8) Deux observables dans les ollisions d'ions lourds ultrarelativistes : La suppression du

J/ψ

et leot

Ph.D. day,Servi e for Theoreti al Physi s ofCEA/Sa lay

Sa lay,Fran e, O t. 20th2000

S9) Collisions d'ions lourds ultrarelativistes : Le ot existe-t-il?

Young resear herseminar of the Servi efor Theoreti al Physi s of CEA/Sa lay

Sa lay,Fran e, Jan. 20th2000 (invited)

I.3 Supervision and tea hing a tivities

I.3.1 Supervision

1) O t 2008  ... 2010 : Ph.D. thesis, S. Vidal, Méthodes hiérar hiques pour la dynamique

d'agrégatsen onta t ave un environnement

2) Mar  Jun 2008 : Graduate internship (Physi s of Matter), S. Vidal, Méthodes hiér

ar- hiques pourla dynamique d'agrégats en onta t ave unenvironnement

3) June 2008 : Undergraduate internship, S. Gar ia (É ole Normale Supérieure of Ca han)

andO.Chabiron(FundamentalPhysi s,UniversityofToulouse3),Simulationdel'irradiation

d'agrégatsde sodium par unlaser à éle trons libres

4) MayJune2004: Mastertraining(FundamentalPhysi s),A.Bail,Modélisationnumérique

d'un agrégat d'argon

I.3.2 Tea hing

•

In hargesin e2007 ofthe ourseTools forStatisti al Physi s, L3Physique Fondamentale, Univ. PaulSabatier, Toulouse

•

In hargesin e2007ofboth oursesAnalyti almethodsforphysi istsetComputermodelling andsolutionsofproblemsinphysi s,L2Physique,ChimieetAppli ations, optionPhysique,

Univ. PaulSabatier, Toulouse

•

In harge from 2003 to 2007 of the ourse Analyti al methods for physi ists, L2 Physique, Chimie etAppli ations, option Physique, Univ. Paul Sabatier,Toulouse

•

Sin e2002: TutorialsofNon-linearphysi s,M1Physique Fondamentale,M1astrophysique etM1 Atmosphère-O éans-Continents, Univ. PaulSabatier, Toulouse

•

Sin e 2002 : Computer tutorials of Non-linear physi s, M1 Physique Fondamentale, M1 astrophysique etM1 Atmosphère-O éans-Continents, Univ. PaulSabatier, Toulouse

•

Sin e 2007: CourseofTools forStatisti al Physi s, L3Physique Fondamentale, Univ. Paul Sabatier, Toulouse

•

Sin e 2002 : Tutorials of Tools for Statisti al Physi s, L3 Physique Fondamentale, Univ. PaulSabatier, Toulouse

•

2002  2006 : Computer tutorials ofStatisti al Physi s, L3 Physique Fondamentale, Univ. PaulSabatier, Toulouse

•

Sin e 2002 : Tutorials ofAnalyti al methods for physi ists, L2 Physique, Chimie et Appli- ations, option Physique, Univ. Paul Sabatier,Toulouse

•

2002  2006 : Computer tutorials of S ienti Cal ulus, L2 Physique, Chimie et Appli a-tions, optionChimie, Univ. Paul Sabatier,Toulouse

•

2002  2003 : Tutorials ofSolid me hani s,DEUG SM, Univ. Paul Sabatier, Toulouse

•

20072008 : Tutorials ofthermodynami s, L1 Chimie-Biologie-Physique-Santé, Univ. Paul Sabatier, Toulouse

•

20032006: TutorialsofGeneralPhysi s,L1Chimie-Informatique-Mathématique-Physique, Univ. PaulSabatier, Toulouse

Thesis

Contents

II.1 Dynami sof lusters in onta t with an environment. . . 12

II.1.1 Startings ienti ontext . . . 12

II.1.2 Hierar hi alapproa hesforthedes riptionof lustersin onta twith anenvironment . . . 12

II.2 Complementary resear ha tivities . . . 13

II.2.1 Dynami alself-intera tion orre tion . . . 13

II.2.2 Extensiontoorgani mole ules and lusters . . . 14

II.2.3 Detailedanalysisofthedynami soffreeirradiated lusters . . . 17

II.3 S ienti proje t . . . 19

II.3.1 Metal lustersadsorbedatdefe ts onMgO(001) . . . 19

II.3.2 Heliumsurrounding . . . 19

II.3.3 Chromophoreee tsin irradiatedwater lusters . . . 20

II.3.4 Irradiationof lusters bylaserlightunderextreme onditions . . . . 21

II.3.5 Developmentofsoftwares . . . 22

This haptersummarizes mys ienti a tivities duringthelast seven years. Aparti ular

fo us lies on the development of a hierar hi al method to des ribe the intera tion of metal

lusters with a substrate with dynami al polarizability (see Se . II.1 and Appendix A). In

a se ond se tion, I briey present omplementary resear h a tivities, espe ially sin e 2005.

FinallyI give some perspe tivesinthelast se tion.

NotaBene: The itationsinarabi gures(asforinstan e[16℄) orrespondtomyarti les,

II.1 Dynami s of lusters in onta t with an environment

II.1.1 Starting s ienti ontext

I arrived in 2002 in Prof. E. Suraud's group, in the Laboratory for Theoreti al Physi s of

Toulouse,UniversityPaulSabatier(Toulouse3)andgotapermanentpositionasanassistant

professor in 2003. The Finite Fermioni Systems group onsisted in Prof. E. Suraud and

Prof. M. Belka em, and had already at that time a ri h experien e on the dynami s of

free metal lusters under irradiation. However Prof. M. Belka em's departure in Sep. 2005

strongly weakened the group. Nevertheless, the longstanding and a tive ollaboration with

Prof. P.-G. Reinhard from Erlangen University(Germany) allowed our group to maintain a

highlevelofs ienti produ tion.

The ore a tivity of our group on erns the mi ros opi des ription of the dynami s of

lusters andmole ulessubje tto violent ele tromagneti perturbations, su h asdeliveredby

short and intense laser pulses or highly harged ioni proje tiles. From the formal point of

view,density fun tionaltheory (DFT) [Hoh 64,Par 89,Dre 90,Koh 99℄has evolved overthe

lastde adestoastandardtheoreti altoolforthedes riptionofele troni propertiesinmany

physi al and hemi al systems,espe ially in systemswith sizeable numbers of ele trons. Its

time-dependent version(TDDFT)[Run84,Gro 90,Mar 04℄isamore re ent a hievementand

stillmotivatingmanyinvestigations,bothforformalandpra ti alaspe ts[Mar06℄. TDDFT

oersauniqueandversatiletoolforthedevelopmentofseveraltheoriesintherealmofviolent

dynami als enarios in irradiated free metal lusters, from fullyquantum to mostly lassi al

approa hes [Rei 03℄. In parti ular, the treatment of the valen e ele trons of the luster by

TDDFT, oupled non-adiabati ally to mole ular dynami s (MD)for the luster ions, allows

usto explore manypossible s enarios ofirradiated lusters and mole ules, fromthelinearto

thehighlynon-linearregime. Ourgrouphasmeanwhile worked outaplatformofveryrobust

andexiblehomemadenumeri al toolsdeveloped overtheyears[Cal00℄. Onlyfewgroupsin

theworld an a tually ompete withsu h ami ros opi des riptionof non-linear pro esses.

II.1.2 Hierar hi al approa hes for the des ription of lusters in onta t with

an environment

In2002,thesemethods werealreadywell validatedinthe aseof freemetal lusters [Cal00℄.

Thiss ienti ontext was thus favorable for newmethodologi al developments, asthe

on-stru tion of dynami al hierar hi al approa hes to des ribe the oupled responseof a luster

in onta twithanenvironment. Thistopi hasbeenthe oreofmyresear ha tivitiesduring

the last years. The physi al motivation of our investigations was the understanding of the

dynami s of lusters and mole ules in onta t witha substrate, a situation whi h o urs in

numerous physi al ontexts, ranging fromsurfa e physi s to water-embedded biologi al

sys-tems. Whileenvironmentsmayhelp ontrollingexperimental onditions,su hasforexample

onsurfa es, they also make thedes riptionof the system mu h more involved, pre iselydue

tothepresen eoftheenvironmentwhi hmayplayanon-negligibleroleintheresponseofthe

systemtoanexternal perturbationsu hasanirradiation. Nevertheless,standardapproa hes

donottakeintoa ount thedynami alpolarizabilityoftheenvironment. Wehavethus been

ledto develop amore sophisti ated modela ounting for su hdegrees of freedom.

We rst developed sin e 2003 a hierar hi al modeling of metal luster in onta twithan

argon substrate (surfa e or matrix) [Feh 05,Feh 06a,Feh 06b℄. While the luster is treated

inTDDFT-MD as before, the environment is des ribed at a lower level of sophisti ation in

the spirit of QM/MM (Quantum Me hani s/Mole ular Me hani s) approa hes of quantum

tion by attributing dynami al dipoles to ea h atom of theenvironment. These new degrees

of freedom turn out to be a key issue for the des ription of irradiation pro esses, espe ially

when hargesareinvolved, eitherbe ause ofdealing with harged spe iesor asaresultof an

irradiationpro ess. Themanyresultsobtaineddemonstrated aposteriorithekeyimportan e

of this aspe t, whatever the dynami al regime under onsideration. We later extended our

hierar hi al methodto otherraregases(Ne,Kr)[18℄,andto ame hani allyharderinsulator,

thatisMgO [Bar07a,Bae 08℄.

The results of our hierar hi al methods applied to various s enarios (neutral or harged

lusterdeposition on a surfa e,Coulomb explosion ofembedded lusters after irradiation by

anintenselaser,photoele tronspe tros opyofdeposited lusters,...) represent11published

arti les in luding 1 review [1,5,7,10,1319℄, 1 submitted arti le [34℄ and 2 in preparation.

Thereviewarti le [5℄ anbefoundintheAppendix A. Forthesake ofbriefness,wereferthe

reader tothis appendix foran exhaustive reportof our models andresults on thistopi .

II.2 Complementary resear h a tivities

Sin e 2005, we also developed new a tivities along three omplementing lines : i) Formal

developmentsforthe orre tdes riptionofionization dynami sintheframeworkofTDDFT;

ii) Te hni al and numeri al extension of the non-adiabati des ription of ele tron dynami s

to the ase of organi systems; iii) Elaborated study of the dynami s of free lusters under

extreme light irradiation. All three aspe ts have been su essfully worked out over the last

fewyears. Theyarebriey dis ussedbelow andillustrated bya fewtypi al results.

II.2.1 Dynami al self-intera tion orre tion

A orre ttreatment ofionization pro essesin TDDFTis still raisingsizeable di ulties,

es-pe ially from the formal side. Indeed, standard DFT approa hes rely on the lo al density

approximation (LDA) whi h is plagued by the well known self-intera tion problem, that is

theself-intera tionofanele tronwithitselfthroughthetotaldensityfromwhi htheele tron

potential is built. There is thus a ru ial need to over ome this problem inorder to re over

properlyionization properties, espe iallywhen onsidering expli ittime-dependentpro esses.

Akeypoint thus on erns a leanformulation oftheself-intera tion orre tion (SIC)method

ontopofthestandardLDAofTDDFT,see[Mar06,Kue08℄andreferen estherein,forre ent

reviewsonthe topi . Whiletheproblemiswell studiedinthestati domain, time-dependent

versionsof the theoryhave only been developedintheframework offurther approximations,

espe iallywithin theoptimized ee tivepotential (OEP) strategy. The rsttaskwas thus a

leanreformulationoftime-dependent SIC(TDSIC)inwhi hanexpli ita ountof

orthonor-malizationwasin ludedinthe theory[8,9℄. The TDSICequations arerather involvedandin

order to be able to have a propertime propagation, we have been led to introdu e two sets

ofsingle ele tron orbitals. Su h a strategy amountsto exploit the usuallyleft-overdegree of

freedom ofunitary transformamongst ele troni orbitals intimepropagation, anidea whi h

hadneverbeenputforward. Theresultled,tothebestofourknowledge,totherst omplete

al ulationoffullTDSIC,whi histhusprovidingaben hmarkforthedevelopmentoffurther

approximations.

This double set strategy also turned out to be extremely useful for the stationary limit

asit provided the basi idea for developing e ient and simple approximations of the OEP

methods builtontop ofSIC.Thisallowed toproposeanew,e ient SIC-OEPs hemewhi h

turnsout to provide remarkably a urate resultsfrom a rathersimple treatment [4,11℄. The

orbitals (whi h allow to properly ensure orthonormalization), while the se ond one leads to

more delo alized orbitals typi al of bonding orbitals. An illustration of our simplied

SIC-OEPwith the double set strategy (Generalized SIC-Slater) is given inFig. II.1and applied

to the luster Na

5

in a dynami al situation [2℄. The initial ex itation is a small boost of

Figure II.1: Total energy and dipole moments,

hxi

and

hyi

, as a fun tion of time, after an initial small boost of groud-state ele troni distributions of Na

5

. Are ompared standard (one-set)SIC-Slater andour simplied two-set SIC-OEP,Generalized SIC-Slater [2℄.

the initial (ground state) ele troni distributions of Na

5

. This simulates a very short laser pulse and still allows to he k energy onservation in time. Time evolutions of the total

energyandthedipolemomentsareplotted and ompared withstandard (one-set)SIC-Slater

approximation. It is well known that this approximation suers from in onsisten ies in the

timedomain,asit an stronglyviolate energy onservationand zerofor etheorem[Mun07℄.

As it is obviously visible in Fig. II.1, the range of stability (that is, time of energy-stable

propagation)is dramati allyenhan ed byGeneralized SIC-Slater,while standard SIC-Slater

diverges at very shorttimes.

The full TDSIC and its simplied SIC-OEP version have been applied with su ess to

various physi al systemsin luding metal lusters, organi mole ules and quantum dots, and

ledto6publi ations[2,4,8,9,11,12℄,and2inpreparation. Thenextstepto omeistodevelop

asimplied and robust versionof thetheoryto be usedinlarge s ale al ulations, sin e our

s hemes,even intheir simpliedversion,arestill highlytime- onsuming.

II.2.2 Extension to organi mole ules and lusters

Whilewe ontinuedtoinvestigateourmodelinthe aseof luster/substrate ombinations,we

approa hes ompatiblewithourstrategy. Still,dis ussionswithseveral olleaguesworkingon

the irradiation of small organi /biomole ules led us to postpone theimplementation of this

extension of our hierar hi al modeling to thebenet of more detailed studies of very small

systems,whi hweremore urgentlyinteresting experimental olleagues. Indeedthisturnsout

to provide valuable prototype ases for irradiation studies even when very small. In su h

ases, the system isfully treated at a TDLDA-MD level. SIC is still handled, however in a

simplied way (Average Density SIC, ADSIC [Leg 02℄). This SIC allows to properly treat

ele troni dynami s but failsat des ribing mole ular disso iationquantitatively. Su h

al u-lations, in addition to their intrinsi physi al interest, will furthermore serve asben hmarks

for hierar hi al approa hes to ome.

Theextensionofour TDLDA-MDmethodto organi mole ulesisinprin iple

straightfor-ward but requires some te hni al ne-tuning. Surprisingly enough, su h fully non-adiabati

al ulations allowing to over any dynami al regimes had not been realized before. Only

simplied situations in whi h either ions are kept xed (linear pro esses or very energeti

ollisions)[Yab 99,Hei 00,Var 06℄ or ele trons follow ions at Born-Oppenheimer level were

available for su h systems. The major eort to be done inour approa h on erned the v

ali-dation of pseudopotentials espe ially designed for our grid representation of ele troni wave

fun tions. Pseudopotentialsimplya minimumlength s aleasso iated to theatomi ore size

whi h,inturn, determinesa minimumgrid spa ing. As longasonly onematerial ispresent,

any well behaved (smooth enough) pseudopotential is appli able. In the ase of mixed

sys-tems (as typi al organi mole ules), one has to retune pseudopotentials to a ommon (and

su iently large)minimumlength. Su h ane-tuningwassu essfullydonefor thestandard

organi elements(C,N,O,andH)tobeusedinourtarget mole ules. Of ourse,theretuning

implies some ompromises. But these are bene ial to attain representations whi h allow

robust al ulationsoverlongtimes andinthenon-linear domain.

The new set of pseudopotentials was then used to study the dynami s of small organi

systems espe ially under laser irradiation and ollisions with harged or neutral proje tiles.

We studied the laser irradiation of theethylene mole ule extensively; two arti les reporting

our ndings have been submitted [32,33℄. In lose ollaboration with Prof. M. Farizon's

experimental groupattheInstitutefor Nu learPhysi s ofLyon(IPNL), withwhi hwe have

ajoined ontra tfromthe Fren hNationalAgen yforResear h(ANR),we havealsofo used

on the irradiation of simplest water mole ules lusters. A ommon arti le on ollision of a

mole ule water witha proton at low velo ity or a neutral arbon atom at highvelo ity has

been published re ently [6℄. The full non-adiabati oupling between ele trons and ions is

here ru ialasitallowsto overanydynami alregimeintheeld, namely hargedorneutral

proje tiles at low or high velo ity, a possibility whi h, to the best of our knowledge, is a

premiere inthe eld[Gai07,Koh 08℄.

Further results on irradiation of small harged water luster are urrently available and

arebeingpreparedfor2publi ations. Asanillustration, wepresentinFig.II.2thedynami s

of(H

2

O)H

3

O

+

irradiated bylaserswithintensity

I = 2 − 7 × 10

14

W/ m

2

,full widthat half

maximum (FWHM) of 20 fs, and three dierent frequen ies (far IR, opti al, XUV). In the

opti al domain, the ele troni dipole ni ely follows thelaser pulse, and ele troni ex itation

endsas soon asthelaser is swit hed o. This pattern is very similar to what is observed in

metal lusters when irradiated by anopti al laserwithfrequen y otheplasmonresonan e.

Asexpe ted, no ele troni emission isobserved,sin e water is an ele troni insulator with a

gap ofabout 10eV.Only aslight luster rotationisindu ed. Similar behaviorsareobserved

withUV frequen ies (not shown). For XUV frequen ies, whi h lie inthe opti al absorption

regimeof (H

2

O)H

3

O

+

,signi ant ionization o urs (

∼ 1

ele tron)and the hargeinstability provokes aCoulomb explosionofthe luster. Notealso theunusual dipoleresponse pattern,

-0.15

-0.1

-0.05

0

0.05

0 10 20 30 40 50 60

x

dipole (a

0

)

time (ps)

I=7I

₀

ω

=24 eV

N

_esc

≈

1

-0.04

-0.02

0

0.02

x

dipole (a

0

)

I=2I

₀

ω

=2.72 eV

N

_esc

≈

0

-0.04

-0.02

0

0.02

0.04

x

dipole (a

0

)

I=4I

₀

ω

=0.4 eV

N

_esc

≈

0

0 10 20 30 40 50 60

-2

0

2

4

6

8

x

coord. (a

0

)

time (ps)



H

₃

O

+



H

₂

O

-1

0

1

2

3

4

5

x

coord. (a

0

)

-1

0

1

2

3

4

5

x

coord. (a

0

)

Figure II.2: Irradiation of (H

2

O)H

3

O

+

by lasers with polarization along

x

axis, FWHM of 20fs, intensitiesof about

I

0

= 10

14

W/ m

2

,and threefrequen ies asindi ated. The number

of es aped ele trons

N

esc

is also reported for ea h ase. As a fun tion of time : Ele troni dipolemomentin

x

dire tion(left olumn),andioni

x

oordinates(right olumn). Thedark (blue)lines orrespondto theioni positions ofH

3

O

+

,whilethelight(green) onesshowthat

soonasele tronsareemitted. InthefarIRdomaininstead,thewater lusterisstablebutioni

vibrations showup after 30 fs, while still no ele troni emission isobserved. This frequen y

s anthusni elypresentsthevariousdynami al ouplingsbetweenalaserandawater luster.

Asystemati studyonlargerwater lustersisinprogress. The aseofirradiationbya harged

proje tile isalso urrently investigated.

II.2.3 Detailed analysis of the dynami s of free irradiated lusters

Inparalleltothese(sometimesheavy)theoreti aldevelopments,wehave ontinuedtoanalyze

some detailedaspe ts of oupledele tron and iondynami s infreeirradiated metal lusters,

motivated bynew hallenging experimental developments. Indeed, thenew developments in

laser te hnology allow growing availability of light under extreme onditions : Attose ond

pulses, and high photon frequen ies delivered by free ele tron lasers (FEL). Moreover new

experimental detailed data on properties of distributions of emitted ele trons (high-order

harmoni generations, angular-resolved photoele tron spe tra, time-resolved photoele tron

spe tra) allusforpursuingourstudiesonfreeirradiated lusters[Sur05,Rei05,Nes06,20,21℄.

In parti ular, non-linear intera tions between an intense laser eld and a dense luster

matter onstitute a topi of high urrent interest in whi h many investigations have been

arriedoverthe past years (fora re ent review, see e.g. [3℄). For instan e, these intera tions

an produ e an enhan ed high-order harmoni generation (HHG), ompared with the ase

of irradiation of atomi jets. HHG have been observed in a few experiments on rare gas

lusters[Don96,Tis97,Vel01,Pai06℄. Ithasalsobeenobservedinorgani mole ules[Lev01,

Ita04℄. Howeverthetheoreti alexplorationofasu haphenomenonformultiele tronsystems

isstill adeveloping domain,sin e omputationsinfull time-dependent S hrödinger equation

areverytime- onsuming. ThusTDLDA-MDappearsasapowerfultooltoelu idatethisissue

inlarge systems.

As an example, we simulated mole ular HHG (MHHG) obtained after irradiation of an

ethylene mole ule by a one- olor laser (frequen y of

ω

1

= 2.72

eV, intensity of

I

1

= 10

14

W/ m

2

,rampprolewithwholeduration of30fs,polarizationalongC-Cdoublebond

dire -tion)andatwo- olorlaser(same

ω

1

and

I

1

for therst olor,but

ω

2

= 2ω

1

and

I

2

= I

1

/4

for these ond olor,and norelativephase; sametimeproleandpolarization)[33℄. TheMHHG

spe trumof C

2

H

4

,obtained afterintera tion withtheone- olor laser,is more or lesssimilar tothatofanatom. Atvarian e,afterthe two-frequen ylaserirradiation,theMHHGpattern

strongly diers. To geta deeperinsight of these dis repan ies,we performeda Gabor

trans-Figure II.3: Time prole of the 5th harmoni obtained by Gabor transform of the dipole

moment of C

2

H

4

along the laser polarization dire tion (same asthe C-C double bond one), after irradiation by a one- olor laser (

ω

1

= 2.72

eV,

I

1

= 10

14

W/ m

2

, solid line), and a

form of the dipole moment

D(t)

. The latter is dominated by the response along the laser polarization, denoted in the following as

D

pol

. The Gabor transform onsists in a Fourier transform where the fun tion to transform is multiplied by a Gaussian, viewed as a time

window. Morepre isely, we ompute the fun tion

D

G

(ν, τ ) =

R

d

t D

pol

(t) e

2πiνt

_e

−(t−τ )

2

/2σ

2

,

where

σ

is hosen asone-tenth of the laseropti al period. Thistime-frequen y analysisthus provides time proles of the dierent harmoni s

ν

. As an illustration, we plot

D

G

(5, τ )

in Fig. II.3. The 5th harmoni , in the one- olor ase, smoothly evolves in time, indi ating a

multiphoton me hanism. When the two- olor laser is used instead, the yield is higher and

exhibitsni eos illationsinphasewiththelaseropti al y les. One anexplainthis behavior

byre ollisions ofthe ele troni wave pa ketwiththeioni ores.

Thedetailedstudyofphotoele tronangular distributions(PAD) analso shedsome light

on the dynami s of photoemission, in parti ular regarding the symmetry of the ele troni

wave fun tionsand thedegree of thermalization. A few highlydetailed experimental results

starttobeavailableintheopti aldomain[Kos07,Bar09℄. Anexampleofsu hananalysison

Na

−

58

ispresentedinFig.II.4. Comparisonwithour al ulationsisdrawnand fairagreement

FigureII.4: Experimentalphotoele tronangulardistributions(PAD)ofNa

−

58

afterirradiation byalaserof intensitylessthan

10

10

W/ m

2

,anda frequen yof4.02 eV (bottom)or2.48 eV

(middle)[Kos07℄. Experimental resultsare ompared withatheoreti al PAD(top)obtained

withalaserfrequen yof

ω = 2.48

eV.Theverti allinesinthelowerpanelindi atethestati single-parti le energies, withanadditional ontribution from

ω

(unpublished).

isfoundbetween theoryandexperiment. A ompleteinvestigationwillbereportedinapaper

inpreparation.

It is also interesting to explore PAD for the ase of irradiated deposited lusters. Su h

al ulationsareunderwayinthe aseofsimple metal lusters depositedoneitheran Arora

MgOsurfa e (inpreparation).

halleng-domain. We have thus startedto ompute the response of (organi and metal) lusters and

mole ulestovery highlaserfrequen ies, fo usingonthedetailedanalysisofthepropertiesof

emitted ele trons,and PADinparti ular.

II.3 S ienti proje t

As exemplied in Se s. II.1 and II.2, the elaborated TDDFT-MD odes developed in our

group over the years oer a unique numeri al tool to explore many non-linear s enarios in

lustersand mole ulesunderextreme onditions, pro esses thatareusually not a essibleby

otherte hniques. Theyalso onstitute agreatopportunitytotest intrulyrealisti situations

the appli ability of formal developments from a numeri al standpoint. We also have

long-standing onta ts withexperimentalgroupsworkinginrelatedelds,for instan einRosto k

(Germany) andLyon(Fran e). Thisprovidespromising opportunitiesfor theappli ations of

thedeveloped formalisms. Following these onsiderations, wehave identied several

omple-mentary axes of work. Three of them relyon thehierar hi al methods developed duringthe

last years. The fourthone fo uses onfree luster dynami s irradiated byextreme light. The

last topi on erns numeri al and formaldevelopments of our odes. We shortly present all

ofthem inthe following se tions.

II.3.1 Metal lusters adsorbed at defe ts on MgO(001)

Whereasthe dynami sofNaatom/ lustersin onta twithararegasenvironment(deposited

or embedded) hasbeen extensively explored [5,7,10,1319℄, the aseofMgO(001) stilloers

manyinterestingdynami als enariostoexplore. Indeed,metaloxidesareofgreat

te hnologi- alimportan einsurfa es ien eandengineering,espe iallyfortheir appli ationsin atalysis

pro esses, prote tive oatings, and mi roele troni s [Hei 94,Woo 01℄. It has been moreover

demonstrated experimentally that defe ts at the MgO surfa e an a t as strong nu leation

anddiusion sites[Als88,Meu94,Haa 00℄. Thishasalso been investigated theoreti allybut

only in stati al ulations [Yan 02,Vit 05,Inn 06,Hon 07,Bar 07b℄. Within our

hierar hi- almodel, we an easily explore dynami al deposition/diusion of Na lusters on neutral or

harged oxygenva an ies, and fullyappre iate theee t of thedynami al polarizabitility of

theoxygen atomsin thesepro esses.

II.3.2 Helium surrounding

Chemi al physi s of ultra- old atoms and mole ules represents nowadays a growing eldfor

the exploration of a large variety of phenomena, e.g., formation of metastable mole ular

omplexesor hemi alrea tionsunderextremely well-dened onditions(temperature,

orien-tation,distributions of populated states). Superuid heliumnanodroplet beams nowprovide

a powerful toolfor hemi al and physi al investigations at very low temperatures for a wide

rangeof embedded mole ules and lusters.

IntheANR ontra tMIRRAMO,joinedwithProf.Farizon'sexperimentalgroupinLyon,

we aim at elu idating at the mi ros opi level the damage on water- oated biomole ules

when intera ting with a high-energy proje tile. The next step in this experiment is to use

embedding in rare-gas (helium or argon) droplets to ontrol the external onditions under

whi hirradiation takespla e. From thetheoreti alpoint of view,the simplestassumption is

that therare gas mostlyprovides a low temperature heat ( old) bath. But a highpre ision

des riptionhasalsoto a ount for theside-ee tsdueto theembedment. Thisthus allsfor

Ele troni spe tros opy inhelium droplets Wehavealreadyperformeddetailed

stud-iesoflowenergyobservables(stru tures,opti alresponse)forsimplemetal lustersin onta t

withraregasenvironments(Ar,Kr, Ne)andfoundthat,inspiteoftheirinert hara ter, rare

gases do ontribute [17℄. However there is only a weak inuen e on the opti al response

of the embedded luster and on ele troni transport, in agreement with experimental

nd-ings[Die02℄.

Still many experimental and theoreti al worksexist for ele troni spe tros opy of doped

helium droplets (see [Sti 01,Sti 06℄ for re ent experimental reviews). For instan e, ex ited

states of benzene [Log 07℄ or Ag atoms [Evg 08℄ embedded in helium droplets have been

exploredexperimentally,and measurements of metastable states have been reported. In the

same spirit,it hasbeen observed very re ently bymeans of pump-probe te hniques thatthe

intera tion of Mg with He an lead to metastable Mg omplexes, with a delayed ollapse

whenirradiated byalaser[Prz08℄. Thesendingshavebeen onrmedtheoreti allybyDFT

al ulations[Her 08℄.

Hen e,regardingthenumerousworksusingheliumsurroundingforthestudyofele troni

properties, the alibration of the potentials between Na and He in our hierar hi al method

will denitely add versatility to our model. The basis of modeling will remain the same as

before, thatisthedes riptionofheliumby lassi alatoms dressedwith( lassi al)dynami al

polarizabilities. There exist,in addition, re ent detailed experimental measurements on

Na-doped helium droplets [Log 08℄, whi h will allow the ne-tuning of the parameters of our

model.

Highenergyex itationsinheliumdroplets Attheotherlimit,weaimatdes ribingthe

mi ros opi me hanismsinvolvedinthe irradiationofmole ulesembedded inheliumdroplets

in the non-linear regime, more losely to Prof. Farizon's experiment. The strategy here is

to des ribe the intera tion of an organi system with a He environment, and thereafter the

time evolution after ollision with an energeti proton. New developments and alibration

in detail will be needed here and will probably ask for more eort, sin e one has to dene

modelpotentials for the various ombinations of C, N,O, H and raregases. We will relyon

ben hmark omputationsfrom the literature, espe iallyfromab-initio quantum hemistry,if

available. We also have the apability to perform our ownab-initio al ulations and will do

thatifne essary. Finalre-tuning of modelparameters allows intheend of thepro ess to t

available experimental resultson su h mixedsystems.

II.3.3 Chromophore ee ts in irradiated water lusters

When, in2005,we aimed atextending our hierar hi al methodofsodium lusters in onta t

withaninsulatorsubstratetothe aseoforgani systemsin onta twithapolarenvironment,

westartedinthesame spiritafewstudiesofNaandNa

2

embedded inwater lusters. Indeed someexperimentalandtheoreti alinvestigationsareavailable(seee.g.[S h03,Bao07,Cwi08,

Kry09℄). Notethat,atvarian ewiththeexothermi rea tionbetweenalkalimetalsandwater,

singleNa atoms donot rea t withH

2

Omole ules or lusters.

However, asmentioned inSe . II.2.2, we postponed the alibration of su h a theoryand

preferred to des ribe the water mole ules at the same level of renement as the embedded

mole ule. Indeed in Prof.Farizon's experiments, the numberof oating water mole uleswill

be pre isely ontrolled (from 2 to about 30). Hen e water will not a t as a ma ros opi

environment but rather asanite systemin onta twiththebiomole ule understudy.

TheexplorationofaNaatom embedded inawater lusterre ently gainedahighinterest

ele trons(LEE).Thelatterareprimaryprodu edbyanirradiation,astheintera tionwithfast

proje tiles duringradiotherapy[San05℄. Theunderstandingand the ontrolofthe hemistry

indu ed by LEE produ ed in biologi al ells is thus of utmost importan e. Very re ently,

L. San he et al. reported that in the presen e of gold nanoparti les, the amount of LEE

reated by a high energy radiation near DNA onsiderably in reases and thus auses mu h

more damage [San 09℄. What is observed here is a hromophore ee t of the gold luster.

Indeed thegold luster, onstitutinganele tron reservoir, an easily ouplewithan external

ele tromagneti eld, and thus an be highlyionized.

The theoreti al des ription of su h a phenomenon is not possible nowadays for su h a

largesystem(gold luster-DNA omplex), sin eele troni emissionisinvolved andthus alls

foradetaileddes riptionofthe ionization. However, withinTDDFT-MD,we anexplorethe

underlying me hanisms byinvestigating theirradiationbyanopti al laserofa simpler atom

embedded in a water luster. The idea here is to gently deposit a small amount of energy

in an organi system, by means of a ( heap) opti al laser, via the preferrential oupling of

a metal atom with the lasereld. LEE an hopefully be emitted from themetal atom, and

provokeafragmentation ofthe water luster,inlinewiththedisso iativeele tronatta hment

observed bySan he et al.. Work inthatdire tion isunder way.

II.3.4 Irradiation of lusters by laser light under extreme onditions

High-intensityX-ray/XUV FreeEle tronLasers(FEL)arenowavailable andwill allownew,

possibly time-resolved (TR), spe tros opies for imaging the ele troni motion on its natural

time-s ale and at the length-s ale of a mole ule. Furthermore, theavailability of attose ond

pulses will even redu e the time s ale at whi h dynami s will be resolved. While there was

foryearsnourgent need fortheoreti alstudiesinthatregime, there ent newexperimentsin

theseeldsopenex itingareasin lusterandmole ularphysi s. However,a uratetheoreti al

des riptionsarestillmissing. Indeed,intenseeldsasprovidedbytheselasersinevitablyex ite

omplexdynami s. Thesu essofimagingte hniquesdependsonour understandingofthese

largelyunknowndynami s, reatingdemandforthetheoryof omplexpolyatomi systemsin

non-perturbative and ultrashort externalelds.

Some onta t with Dr. F. Lépine's experimental group at the LASIM in Lyon (Fran e)

havebeenestablishedthisyearands ienti ollaborationsareexpe tedto ome. Thisgroup

aimsat developing an experiment on C

60

ombining attose ond pulsesand modern imaging dete tion te hniques, to investigate ultrafast multi-ele tron dynami s in omplex isolated

systems. Fromthe experimentalstandpoint,C

60

isa wel ometest asesin e it an beeasily produ edwithnoneedformasssele tion. Atthesideoftheory,itappearsasagood andidate

for theoreti al investigations be ause of its highsymmetry,still keeping the omplexity of a

largemultiele tron system. Up tonow, noexperimenthasexploredextreme lightex itations

inthehighlynon-linear dynami alregime inC

60

,andfurthermore on asub-fs times ale. Produ tionofexperimentaltime-resolvedphotoele tronspe traofC

60

isextremely promis-ingforus. Ourpreviouslydevelopedtheoreti alandnumeri altoolsareideallysuitedtota kle

theopeningissuesofthedynami sof lustersandmole ulesinextreme light. Thesimulation

of the dynami s of irradiated C

60

is a tually essentially a matter of omputing time. One of our goals herewill be to establish time-resolved photoele tronspe tra and angular

distri-butions of ele trons emitted after the intera tion of C

60

(or another luster/mole ule) with an extremely short-pulse and/or a high-frequen y laser. This will allow us to explore the

II.3.5 Development of softwares

Our platform of TDDFT-MD odes allow us to explore inprin iple many dierent types of

dynami alsituations whi h are sket hed inFig.II.5. However, our numeri al toolshas been

(H

2

O)

n

(H

2

O)

n

H

3

O

+

free Na

n

MgO

free CNOH lusters

Ne,Ar,Kr

Opti al response Photoele tronspe tra

Photoele tronangular distributions Clusterdeposition

on insulatorsurfa e Coulomb explosion after laserirradiation

Collisionwith neutralproje tileathighvelo ities hargedproje tileat lowvelo ities Stru ture optimization linear non-linear Collision with harged proje tile athighvelo ities Collision with neutral proje tile atlowvelo ities

Figure II.5: Top : Various luster/environment ombinations that an be studied by our

TDDFT-MD odes. The thi k arrows indi ated the ases des ribed within our hierar hi al

method. Bottom: Dynami alpro esses that an be simulated withour TDDFT-MD odes,

fromstati s and thelinear regimedownto the highlynon-linear domain.

developedovertheyearsinthegroupsofProfs.ReinhardandSuraud,with lear purposeson

simulationsof physi al pro esses,and not on withultimate numeri al optimization asarst

task. Thismakesthem hard tohandle for usersfrom outside. Itis timefora lean-up ofthe

ode and possiblysome further optimization,parti ularly withrespe tto parallel exe ution.

Regarding the numerouspossible al ulationsthat our odes an oer,and thepotential

audien e that may be interested to use them, we aim at improving the interfa e and the

optimization of our odes, so that we an propose them as open sour es, similarly to what

have beena hieved with the O topus ode. Tothat end,we willstart during thisfall a lose

ollaboration on this topi with Prof. Reinhard, Prof. F. Calvayra from the University of

Maine(LeMans,Fran e),whoa tuallydevelopedthethree-dimensionversionofour

TDDFT-MD ode during hisPh.D. thesis withProf. Suraud at the end of thenineties [Cal 00℄, and

Prof. S. Contassot-Vivier from the University Poin aré (Nan y, Fran e), who is a professor

in omputers ien e. Thiswill also probably easethe test and theimplementation of formal

developmentsinTDDFT,asTDSICor SIC-TDOEP.Indeed,althoughformalproblems have

However, the implementation of more sophisti ated TDSIC than ADSIC, as it is urrently

usedin almost all presented results, will allow to upgrade thetreatment from qualitative to

quantitative des riptionof disso iationof systems,espe iallyorgani ones.

By ombining our various expertises, we arequite ondent that we will be ableto oer

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