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1、The universe = matter Condens matt = atoms + bonding + nonbondingStatics:order,nature,length,strengthDynamics:formation,dissociation,relaxation,vibrationStimuli:P,T,E,B,.The laws and driving forces?2024/9/112024/9/112 2Nonbonding Electronics & Energetics: Progress & prospects孙长庆孙长庆Chang Q Sun Outlin
2、eChallenge&objectiveConcepts&definitionsTheories&applicationsNonbonding&antibondingstatesBrokenbond:surfaceenergetics,sizedependencyBrokenbond+nonbond:GNR,4SProspectsB,C,N,O,F-inducedsuperconductivityNOsignalingandCF4syntheticbloodactantConclusion2024/9/112024/9/113 32024/9/112024/9/114 4ChallengeMa
3、croscopic Macroscopic Mesoscopic Atomistic Atomistic Classical approach for macroscopic scales:Atomistic origin Statistic deviationQuantum approach for atomistic scales:AnisotropicInhomogeneityKinetic LocalizedStrain & trapExternal stimulus4-stageCu3O2bondingkinetics2024/9/112024/9/115 5End,defect,a
4、ndedgequantumtrappingMicroelectronics Microelectronics Reliability Reliability 471580471580(2007(2007) )5 5PRL 99,246102(2007)Int Rev Phys Chem 26,619(2007)ScienceScience307,703307,703(2005)(2005)InsightQuantumorcontinuum?2024/9/112024/9/116 62024/9/112024/9/117 7ObjectivesPredictiveobservationfromt
5、heperspectiveofBond & nonbond formation, dissociation, relaxation, & vibrationandtheassociateddynamicsandkineticsofCharge repopulation, polarization, densification & localizationConcepts(energetics & geometries)(energetics & geometries)Bond:Covalent;ionic;metallicNonbondingunpaired:Graphite(sp2);s-m
6、etalsNonbondinglonepair:F,O,N(sp3)Antibondingdipole:Polarization;vanderWaalsMixture:H-bond,C-HbondBrokenbond:Defect,edge,surface,etcINonbonding&antibondingstatesBond-band-barriercorrelationO2andC2H2adsorptionH-surfacetermination2024/9/112024/9/119 9 2024/9/112024/9/111010NH3&H2O-likeBond-band-barrie
7、rcorrelationC2H2andO2onCu(001)Lonepairvibration,superelasticityandhardness,diamond-metaladhesion II. Broken bond BOLS correlationSkin-depth quantum trappingSurface energeticsMesoscopic size dependencyLow-Dsystems?2024/9/112024/9/111515LowD:Highfractionofatomswithzvaluewithin(0-isolated,12-bulkinteri
8、or)-atomicchain,nanoribbon,NT,rod,dot,surface,interface,pointdefects,etc.Interatomicbonding:Bondsbetweenunder-coordinatedtartomareshorterandstronger!Properties:Quantum/continuum/LBA:Q(z,m,d,Eb;,K,K-1;T,P,E,B,):2024/9/112024/9/111717DerivativesPredictive unification:MC, NT, NW, surface, nanograin, na
9、nocavity, etcMechanical strength Thermal stabilityLattice dynamicsPhoton emission & PAElectronic statesMagnetic modulationDielectrics Transport dynamicsQuantificationEnergy levels of an isolated atomVibration of an isolated dimerSpecific heat per bondSingle bond energy Bonding identities in MC & CNT
10、BOLS and applications2024/9/112024/9/111818Core-shellstructure&layer-resolvedXPSHuangetal,NatMater7(2021)308.Matsuietal,PRL2021.100,207201NanosizedependencyBrokenbondenhancedcatalysis2024/9/112024/9/112121SurfaceenergeticsSurfacehardeningandsoftening2024/9/112024/9/112222NWselasticity2024/9/112024/9
11、/112323Definition2024/9/112024/9/112424Localbondaverage(LBA)2024/9/112024/9/112525ComparisonIII.Brokenbond+nonbondGNR&CNTedgesCN-resolvedC1senergyshiftNanocontactCoulombrepulsion2024/9/112024/9/112626GNREg&edgestatesCN-resolvedcorelevelsshiftandtheeffectiveCNofthefew-layerGraphene2024/9/112024/9/112
12、828Mechanism-edgetrappingandpolarization2024/9/112024/9/1129299/11/20249/11/20243030C-CbondinSWCNTFacts:Yt = 0.3685 TPanm remains constant though Y varies from 0.5 (t = 0.34nm) to 5.5 (t = 0.066nm) TPa Tm = 1593 (tip end) Tm increases with wall thickness.Graphene sheet9/11/20249/11/20243131Solutions
13、9/11/20249/11/20243232Yt (TPanm)or Y(TPa)(Yt)(Yt)1 1= = 0.36850.3685Y = 2.595Y=0.8(Yt)(Yt)1 1= = 0.36850.3685Tip-end melting point Tm,1(z = 2) (K)15931593-215316201620Tube wallTm,1(z = 3) (K)160549326741620m2.55852.55852.55854 42.6050Bond thicknesst1(nm)0.142-Bond length d1(nm)0.116-Bond energy E1/E
14、b1.680.53-RemarksAcceptableXXXCoulombrepulsionatnanometersizedcontactsSuperfluidity,superlubricity,supersolidityandsuperhydrophobicity2024/9/112024/9/1133331.2SuperhydrophobicitycoveringsheetSupersolidity:ultra-elasticity+frictionless“Crystal defects enhance the local density of/surrounding vacancie
15、s-Philip W. Anderson, Science 1 May 2021: 631-632Superfluidity+superlubricityMechanism：ElasticcoveringsheetwithlockedelectricmonopoleIVProspectiveapplicationsB,C,N,O,FinducedsuperconductivityCF4actantONmessagingB-,C-,N-,O-,F-inducedhigh-TcsuperconductivityStrongcorrelationNonbondingstatesnearEFFerro
16、electrics & dielectrics ?CF4andSF6syntheticblood CF4B12 (C4+ + 4F1- + 12Bdipole) SF6B18 (S6+ + 6F1- + 18Bdipole) The sp-orbital hybridization of F atom generates three lone pairs that induce the Bdipole.NOsignalingandlivingcellsConclusionTheoftenoverlookedbrokenbondandnonbondingelectronsdomattergrea
17、tly!2024/9/112024/9/1143432024/9/112024/9/114444非键及能态非键及能态起因起因功能功能应用应用反键偶极子反键偶极子(EF)被近邻高密度电子极被近邻高密度电子极化化功函数降低功函数降低表面偶极层形成表面偶极层形成表面能密度升高表面能密度升高电子冷阴极发射电子冷阴极发射超疏水超疏水,自清洁自清洁电子空穴电子空穴(EF)成键过程中电子转移成键过程中电子转移禁带形成禁带形成禁带展宽禁带展宽光发射和吸收光发射和吸收光子探测光子探测非键孤对电子非键孤对电子(EF)氮氮,氧氧,氟等氟等sp3轨道杂轨道杂化化极化近邻原子极化近邻原子化合物高弹性化合物高弹性红外活性
18、红外活性磁性调制磁性调制非键未对电子非键未对电子(禁带或带尾禁带或带尾)碳碳sp2轨道杂化轨道杂化S金属电子金属电子/悬键电子悬键电子局域钉扎极化局域钉扎极化自旋量子霍耳效应自旋量子霍耳效应表面磁性表面磁性石墨导电石墨导电单层石墨带磁性单层石墨带磁性团簇团簇(表面表面)磁性磁性类氢键类氢键类碳氢键类碳氢键偶极子二次成键偶极子二次成键离子对近邻原子极化离子对近邻原子极化偶极子态减弱偶极子态减弱功函数返升功函数返升化学稳定性化学稳定性表面键网络自封闭表面键网络自封闭抗氧化抗氧化断键断键纳米化纳米化缺陷和断裂形成缺陷和断裂形成强化和缩短近邻键强化和缩短近邻键能量能量,电子和质量局域电子和质量局域高高
19、密密度化度化哈密顿量调制哈密顿量调制结合能结合能,电负性电负性,反应活反应活性性,热稳定性调制热稳定性调制近肤限域扎钉效应近肤限域扎钉效应纳米固体尺寸效应纳米固体尺寸效应力力,热热,声声,光光,电电,磁磁,介电等所有物理化介电等所有物理化学性能调制学性能调制Thankyou!Thermo-mechanicalbehavioroflow-dimensionalsystems:Thelocalbondaverageapproach,ProgMaterSci2021;54:179-307.Sizedependenceofnanostructures:impactofbondorderdeficiency,ProgSolidStateChem2007;35:1-159.Oxidationelectronics:bond-band-barriercorrelationanditsapplications,ProgMaterSci2003;48:521-685.Electronicprocessofnitriding:mechanismandapplications,ProgSolidStateChem2006;34:1-20.断键与非键电子学理论与应用研究初探,湘潭大学学报,2021;3:36-45.2024/9/112024/9/114545
