Atomic Clusters with Unusual Structure, Bonding and Reactivity: Theoretical Approaches, Computational Assessment and Applications PDF
Preview Atomic Clusters with Unusual Structure, Bonding and Reactivity: Theoretical Approaches, Computational Assessment and Applications
Atomic Clusters with Unusual Structure, Bonding and Reactivity This page intentionally left blank Atomic Clusters with Unusual Structure, Bonding and Reactivity Theoretical Approaches, Computational Assessment and Applications Edited by Pratim Kumar Chattaraj Indian Institute of Technology Kharagpur, Kharagpur, India Sudip Pan Institute of Atomic and Molecular Physics, Jilin University, Changchun, China Gabriel Merino Universidad de Merida, Merida, Mexico Elsevier Radarweg29,POBox211,1000AEAmsterdam,Netherlands TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UnitedKingdom 50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates Copyright©2023ElsevierInc.Allrightsreserved. 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Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgeinevaluatingandusing anyinformation,methods,compounds,orexperimentsdescribedherein.Inusingsuchinformationormethods theyshouldbemindfuloftheirownsafetyandthesafetyofothers,includingpartiesforwhomtheyhavea professionalresponsibility. Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors,assumeanyliability foranyinjuryand/ordamagetopersonsorpropertyasamatterofproductsliability,negligenceorotherwise,or fromanyuseoroperationofanymethods,products,instructions,orideascontainedinthematerialherein. ISBN:978-0-12-822943-9 ForinformationonallElsevierpublications visitourwebsiteathttps://www.elsevier.com/books-and-journals Publisher:SusanDennis AcquisitionsEditor:CharlesBath EditorialProjectManager:JudithClarissePunzalan ProductionProjectManager:KumarAnbazhagan CoverDesigner:MarkRogers TypesetbySTRAIVE,India Contents Contributors xi 3. Bimetallic clusters M.MolayemandM.Springborg 1. Describing chemical bonding in exotic systems through AdNDP 1. Introduction 41 analysis 2. Computationalmethods 41 2.1 Energycalculator 42 EdisonOsorio 2.2 Globalstructureoptimization 1. Introduction 1 methods 43 1.1 AdNDPimplementation 2 3. Structuralpropertiesofbimetallic 2. Boronhydrides 3 clusters 44 2.1 ChemicalbondingschemeinB H(cid:1) 4. Conclusions 57 3 y complexes 3 Acknowledgments 58 2.2 IsostructuralrelationshipsinB H References 58 n n series 3 2.3 Electronictransmutation 4 4. Unusual bonding between second 2.4 Chemicalbondingindeltahedral row main group elements B H2(cid:1)systems 5 n n GuruduttDubeyandPrasadV.Bharatam 3. Boronnanowheels 7 3.1 Dynamicbehaviorinsmallboron 1. Introduction 61 clusters 7 2. Low-valentstateofmaingroup 3.2 BoronwheelsmembersofWankel elements 61 motorfamily 7 3. L!E Lcomplexes 63 3.3 Designofsandwichstructures 9 3.1 Carbones:DivalentC(0)systems 63 3.4 Dynamicbehavior 3.2 Borylenes:MonovalentB(I) ofB cluster 13 systems 68 36 4. Summary 13 3.3 Nitreones:DivalentN(I)systems 71 References 15 4. Debatesonthebondrepresentation 80 5. Summary 82 2. Electron delocalization References 82 in clusters 5. Conceptual density functional JoseM.MerceroandJesusM.Ugalde theory and all metal aromaticity 1. Introduction 19 DebolinaPaulandUtpalSarkar 2. Electrondelocalizationinflat clusters 20 1. Introduction 87 3. Electrondelocalizationin(pseudo) 2. Historyanddescriptorsof sphericalclusters 30 aromaticity 89 4. Conclusions 35 2.1 Relativearomaticityindices(4X) 90 Acknowledgments 36 3. Aromaticityinthecontextofmetallic References 36 systems 91 v vi Contents 3.1 Alkaliandalkalineearthmetal 91 3. BenzeneanditsgroupIII–Vpnictide 3.2 Transitionmetal 93 clusteranalogues 140 4. Conclusion 94 3.1 Structuralproperties 140 Acknowledgments 94 3.2 Electronicproperties 142 References 94 4. PolymericgrowthofbenzeneanditsIII–V analogues 143 6. Structural evolution, stability, and 4.1 Structuralproperties 143 spectra of small silver and gold 4.2 Electronicproperties 143 clusters: A view from the electron 5. GroupIII–Vgraphene-likematerialsfrom shell model potentialclusterunits 145 5.1 Monolayerindiumnitridefor PhamVuNhat,NguyenThanhSi, thermoelectrics 146 andMinhThoNguyen 5.2 Mono-andmultilayerthalliumnitride 1. Introduction 99 forthermoelectrics 148 2. Equilibriumstructuresandgrowth 5.3 Othertwo-dimensionalgroupIII–V mechanism 100 materials 151 3. Thermodynamicstabilities 107 6. Conclusions 152 4. Phenomenologicalshellmodel Acknowledgments 152 (PSM) 110 References 153 5. Electronicabsorptionspectra 113 6. Concludingremarks 117 9. M(L)8 complexes (M=Ca, Sr, Ba; Fundinginformation 118 L= PH3, PF3, N2, CO): Act of an References 118 alkaline-earth metal as a conventional transition metal 7. Optical response properties of Hai-XiaLi,Zhong-HuaCui,DandanJiang, some metal cluster supported LiliZhao,andSudipPan host-guest systems 1. Introduction 157 ArpitaPoddarandDebduttaChakraborty 2. Computationaldetails 158 1. Introduction 123 3. StructureandstabilityofM(L)8 2. Computationaldetails 124 complex 159 3. Resultsanddiscussion 125 4. MOsandcorrelation diagram 161 3.1 Geometricalstructuresand 5. Energydecompositionanalysis 162 thermodynamicfeasibilityof 6. M(Bz) :20-electroncomplex 167 obtainingthecorrespondinghost- 3 guestmoieties 125 7. Conclusions 170 Acknowledgments 170 3.2 Opticalandelectronicpropertiesof References 171 theselectedmetalcluster-host complexes 127 3.3 AIManalysis 130 10. Structures, reactivity, and 3.4 EDAstudy 132 properties of low ionization 3.5 TDDFTanalysisoftheguest@OA energy species doped fullerenes complexes 134 and their complexes with 4. Conclusion 135 superhalogen References 136 AbhishekKumar,AmbrishKumarSrivastava, GargiTiwari,andNeerajMisra 8. Group III–V hexagonal pnictide clusters and their promise for 1. Introduction 173 graphene-like materials 2. Computationaltechniques 174 3. LowIEspeciesdoped EshaV.ShahandDebeshR.Roy endofullerenes 175 1. Introduction 139 3.1 Li@C60vsSA@C60endofullerene 2. Computationaldetails 140 (SA=FLi2,OLi3,andNLi4) 175 Contents vii 3.2 Li@C vsLr@C 2.3 H-storageinmolecularclusters 222 60 60 endofullerene 176 2.4 H-storageinmaterials 226 4. Endofullerene-superhalogen 3. Conclusions 232 complexes 177 Acknowledgments 232 4.1 Li@C (cid:1)PF endofullerene References 232 60 6 complex 177 4.2 SA@C dBF endofullerene 13. A density functional theory study 60 4 complex 179 of H + and Li + clusters: Similar 3 3 5. Conclusionsandperspectives 180 structures with different bonding, Acknowledgments 181 aromaticity, and reactivity Conflictofinterests 181 properties References 181 DongboZhao,XinHe,MengLi, 11. Generation of global minimum ChunnaGuo,ChunyingRong, PratimKumarChattaraj,andShubinLiu energy structures of small molecular clusters using machine 1. Introduction 237 learning technique 2. Methodology 238 3. Resultsanddiscussion 240 GourhariJanaandRanitaPal 4. Conclusions 243 1. Introduction 185 Acknowledgments 243 References 243 2. Ourproposedmethodologyand algorithm(parallelimplementation) 187 2.1 Particleswarm 14. Designing nanoclusters for optimization 187 catalytic activation of small 2.2 Fireflyalgorithm 188 molecules: A theoretical endeavor 2.3 ADMP-CNN-PSOapproach 190 3. Computationaldetails 191 AnupPramanik,SouravGhoshal, andPranabSarkar 4. Experimentalsetup 191 4.1 PSO,FA,andADMP-CNN-PSO 192 1. Introduction 247 5. Resultsanddiscussion 192 2. N activation 248 2 5.1 PSO:Boronclusters,B (n=5,6) 192 3. H activation 251 n 2 5.2 CNNandPSO:N2(cid:1),N4(cid:1),Au (n=2– 4. ActivationandreductionofCO 253 4 6 n 2 8)andAu Ag (2(cid:3)n+m(cid:3)8) 4.1 Specificroleofmetalhydrideforthe n m clusters 200 reductionofCO 254 2 5.3 Fireflyalgorithmwithdensity 5. ActivationofO andoxidationofCOon 2 functionaltheory 202 Au nanoclusters 255 n 6. Conclusion 206 5.1 EffectofdopinginAu n Acknowledgments 206 nanoclusters 256 Conflictofinterest 206 5.2 Al(cid:1) anionicnanoclusters:Effectof n References 206 electronspin 257 6. H Oactivation 258 2 12. Studies on hydrogen storage in 7. C–XandC–Hbondsactivation 260 molecules, cages, clusters, and 7.1 C–XbondactivationonAl n materials: A DFT study nanoclusters 260 7.2 CompetitiveH–Xeliminationon K.R.Maiyelvaganan,M.Janani,K.Gopalsamy, aluminananoclusters 260 M.K.Ravva,M.Prakash,andV.Subramanian 7.3 Selectivityofaluminananoclusters 1. Introduction 213 duringelimination 262 2. H-storageinvariousmotifs—Theroad 7.4 SelectiveC–Hbond maprepresentation 214 activation 262 2.1 H-storageinsmallmolecules 215 8. Summaryandfutureoutlook 264 2.2 Hydrogenstorageinmolecular Acknowledgments 265 cages 220 References 265 viii Contents 15. Molecular electrides: An overview 6. Conclusion 308 of their structure, bonding, and Acknowledgments 309 reactivity References 309 RanajitSahaandPrasenjitDas 17. Polarizability of atoms and atomic 1. Introduction 275 clusters 1.1 Electrides 275 SwapanK.Ghosh 1.2 Confinementoftheelectron 275 1.3 Developmentoforganic 1. Introduction 313 electrides 275 2. Basicsofresponsepropertiesand 1.4 Developmentofinorganic polarizability 314 electrides 276 3. DFT-basedapproachtocalculationof 1.5 Towardthemolecularelectride 277 polarizability 314 2. Normsandconditionsofbeinga 4. Polarizabilityofsphericallysymmetric molecularelectride 278 systems:Atomsandatomicclusters 3. Computationalmethodology 279 withinthejelliummodel 317 4. Examplesofmolecularelectrides 281 5. Chemicalreactivityindices-basedroute 4.1 Alkalimetal-doped topolarizability 318 electrides 281 6. Discussiononpolarizabilityvaluesof 4.2 Mg EP,molecularelectrideandsmall atomicclusters 318 2 moleculeactivation 283 7. Concludingremarks 319 4.3 Bondingin[Mg (DippL) ]2(cid:1)complex Acknowledgments 319 4H 2 anditselectridenature 285 References 319 4.4 Mg @C anditselectride 2 60 characteristics 286 18. Advances in cluster bonding: 4.5 BinuclearSandwichcomplexesof Bridging superatomic building alkalineearthmetalsaselectrides 287 blocks via intercluster bonds 4.6 Li @Cg(Cg=B andC )andtheir 3 40 60 electridenature 288 NikolayV.Tkachenko,Zhong-MingSun, 5. Conclusion 289 AlexanderI.Boldyrev,andAlvaro Mun˜oz-Castro Acknowledgments 290 Authorsnote 290 1. Introduction 321 References 290 2. Interclusterbondingofgoldclusters 322 3. InterclusterbondingofZintlclusters 323 16. Hydrogen trapping potential of a 4. Extendednetworks 328 few novel molecular clusters 5. Conclusions 329 and ions Acknowledgments 330 References 330 SukantaMondal,PrasenjitDas,and SantanabGiri 19. Zintl cluster as a building block of 1. Introduction 297 superalkali, superhalogen, 2. Theoreticalbackground 299 and superatom 3. Computationaldetails 301 4. Atomicandmolecularclusters 302 SwapanSinha,RuchiJha,SubhraDas,and 4.1 MgandCaclusters 302 SantanabGiri 4.2 B2LiandB2Li2 1. Introduction 333 moieties 302 2. Computationaldetails 333 4.3 C12N12cage 303 3. Zintlsuperalkali 334 5. Ionicclusters 305 4. Zintlsuperhalogens 335 5.1 N4Li2andN6Ca2clusters 305 5. Zintlsuperatom 339 5.2 Li3+andNa3+ions 306 6. Concludingremarks 342 5.3 B2Li+andB2Li2+ions 307 Acknowledgments 342 5.4 M5Li7+(M=C,Si,Ge)clusters 308 References 342 Contents ix 20. Metallic clusters for realizing 2.4 Temperature-induced planar hypercoordinate second- transformation 381 row main group elements and 3. Perspectivesandconclusions 384 multiple bonded species References 385 AmlanJ.Kalita,ShahnazS.Rohman, 23. Application of frustrated Lewis ChayanikaKashyap,LakhyaJ.Mazumder, pairs in small molecule activation IndraniBaruah,RitamRajBorah, FarnazYashmin,KangkanSarmah, and associated transformations andAnkurK.Guha DandanJiang,ManasGhara,SudipPan, 1. Introduction 345 LiliZhao,andPratimKumarChattaraj 2. Planarhypercoordinatemaingroup 1. Introduction 387 elements 345 2. ThechemistryofLewisacidsand 3. Planarpentacoordinatenitrogen 348 bases 387 4. Metalclustersupportedmultiplebonded 3. IdentificationofFLPreactivity 389 second-rowmaingroupelement 349 4. MechanismofH activationbyFLPs 389 5. Conclusionsandfutureaspects 353 2 5. ThermodynamicsonH activationby Acknowledgment 353 FLP 2 392 References 353 6. Activationofothersmallmolecules 393 7. Aromaticity-enhancedsmallmolecule 21. Planar hypercoordinate carbon activation 397 8. Catalytichydrogenation 398 PrasenjitDas,SudipPan, andPratimKumarChattaraj 9. Boron-ligandcooperation 401 10. Polymerizationreaction 403 1. Introduction 357 11. Summaryandoutlook 407 2. Planartetracoordinatecarbon(ptC) 357 References 407 3. Planarpentacoordinatecarbon (ppC) 361 24. Ligand-protected clusters 4. Planarhexacoordinatecarbon(phC) 365 5. Highercoordinatecarbon 365 YukatsuShichibuandKatsuakiKonishi 6. Conclusion 368 1. Introduction 411 Acknowledgments 369 2. Representativeexamplesoftheoretical References 369 studies 411 3. Diphosphine-ligatedgoldclusters 411 22. Transformation of nanoclusters 3.1 Jelliummodelsandcoreshapes 411 without co-reagent 3.2 Geometricstudies 413 3.3 Electronicstudies 414 SaniyaGratious,SayaniMukherjee, 3.4 Effectsofligandsongeometricand andSukhenduMandal electronicstructures 416 1. Introduction 373 4. Conclusion 420 2. Co-reactant-freetransformations 373 References 420 2.1 pH-inducedtransformation 373 2.2 Solvent-inducedtransformation 375 2.3 Photo-inducedtransformation 379 Index 423
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