量子化學方法的開發及其在能源環境材料研究中的應用-趙焱.pdf

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1、趙 焱 四川大學材料科學與工程學院武漢大學工業科學研究院1匯 報 內 容一量子化學方法的介紹1二量子化學方法的開發三能源環境材料研究中的應用案例2量子化學方法The fundamental laws necessary for the mathematical treatment of The fundamental laws necessary for the mathematical treatment of a large part of a large part of physics physics and and the whole of chemistrythe whole of

2、chemistry are thus completely known,and the difficulty are thus completely known,and the difficulty lies only in the fact that application of these laws leads to equations that are lies only in the fact that application of these laws leads to equations that are too too complex to be solvedcomplex to

3、 be solved.P.A.M.Dirac,1930P.A.M.Dirac,1930EnergyWavefunction 122 122+1The Hamiltonian in atomic units量子化學方法Wavefunction MethodsDensity Functional MethodsWalter Kohn for his development of the for his development of the density functional theorydensity functional theory John Pople for his developmen

4、t of for his development of computational methods in computational methods in quantum chemistry”quantum chemistry”1998 Nobel Prize WinnernHohenbergHohenberg and Kohn(1964)and Kohn(1964)nTotal energy is a functional of the electron density Total energy is a functional of the electron density E E nThe

5、 exact density minimizes The exact density minimizes E E nKohn-Sham Equation(1965)Kohn-Sham Equation(1965)21()(,;)()()2extxciiidrrrrrrr1MextZ rR2()()occjjrrnExact ExchangeExact Exchange*HF*1|ijjijiid 121221211rrrrrrrrrBecke,Phys.Rev.A,1988,38,3098 他引：他引：58641=4/3()4/3()2()1+6sinh1()()=()4/3()=32 34

6、1/3=0.0042a0,ax和ac通過線性最小二乘法擬合56 AEs，42 IPs，8 PAs，10 TAEsBecke,JCP,1993,98,5648,他引：他引：93040 7量子化學數據庫非共價作用非共價作用Benchmark Databases for Nonbonded Interactions and Their Use to Test Density Functional Theory,JCTC,2005,1,415他引：他引：971Computational Characterization And Modeling of Buckyball Tweezers:Densit

7、y Functional Study Of Concaveconvex Interactions,PCCP,2008,10,2813 他引：他引：261Benchmark Data for Noncovalent Interactions in HCOOH Benzene Complexes and Their Use for Validation of Density Functionals,JCTC,2009,5,2726 他引：他引：33化學反應能壘化學反應能壘Benchmark database of barrier heights for heavy atom transfer,nu

8、cleophilic substitution,association,and unimolecular reactions and its use to test theoretical methods,JPC A,2005,109,2012 他引：他引：885The DBH24/08 database and its use to assess electronic structure model chemistries for chemical reaction barrier heights,JCTC，2009,5,808 他引：他引：527主簇化學鍵能主簇化學鍵能Density Fu

9、nctional Theory for Reaction Energies:Test of Meta and Hybrid Meta Functionals,Range-Separated Functionals,and Other High-Performance Functionals,JCTC,2005,1,415他引：他引：199Benchmark Database for Ylidic Bond Dissociation Energies and Its Use for Assessments of Electronic Structure Methods,JCTC,2012,8,2

10、824 他引：他引：33過渡金屬化學反應能過渡金屬化學反應能Benchmark Energetic Data in a Model System for Grubbs II Metathesis Catalysis and Their Use for the Development,Assessment,and Validation of Electronic Structure Methods,JCTC，2009,5,324 他引：他引：347Databases for Transition Element Bonding:MetalMetal Bond Energies and Bond

11、Lengths and Their Use To Test Hybrid,Hybrid Meta,and Meta Density Functionals and Generalized Gradient Approximations,JPC A，2005,109,4388 他引：他引：258Schreiner,Peter R.Relative Energy Computations with Approximate Density Functional Theory-a Relative Energy Computations with Approximate Density Functio

12、nal Theory-a Caveat!Caveat!Angewandte Chemie,International Edition (2007),46(23),4217-4219.Grimme,Stefan;Steinmetz,M;Korth,M.StereoelectronicStereoelectronic Substituent Effects in Saturated Main Substituent Effects in Saturated Main Group Molecules:Severe Problems of Current Kohn-Sham Density Funct

13、ional Theory.Group Molecules:Severe Problems of Current Kohn-Sham Density Functional Theory.Journal of Chemical Theory and Computation(2007),45(27),4460-4464Schreiner,Peter R.;Fokin,Andrey A.;Pascal,Robert A.,Jr.;De Meijere,Armin.Many Density Many Density Functional Theory Approaches Fail To Give Re

14、liable Large Hydrocarbon Isomer Energy Differences.Functional Theory Approaches Fail To Give Reliable Large Hydrocarbon Isomer Energy Differences.Organic Letters (2006),8(17),3635-3638.Wodrich,Matthew D.;Corminboeuf,Clemence;Schleyer,Paul von Rague.Systematic Errors in Systematic Errors in Computed

15、Alkane Energies Using B3LYP and Other Popular DFT Computed Alkane Energies Using B3LYP and Other Popular DFT FunctionalsFunctionals.Organic Letters (2006),8(17),3631-3634Check,Catherine E.;Gilbert,Thomas M.Progressive Systematic Underestimation of Reaction Progressive Systematic Underestimation of R

16、eaction Energies by the B3LYP Model as the Number of C-C Bonds Increases:Why Organic Chemists Energies by the B3LYP Model as the Number of C-C Bonds Increases:Why Organic Chemists Should Use Multiple DFT Models for Calculations Involving Should Use Multiple DFT Models for Calculations Involving Poly

17、carbonPolycarbon Hydrocarbons.Hydrocarbons.Journal of Organic Chemistry(2005),70(24),9828-9834.Izgorodina,Ekaterina I.;Coote,Michelle L.;Radom,Leo.Trends in R-X Bond Dissociation Energies Trends in R-X Bond Dissociation Energies(R=Me,Et,(R=Me,Et,i-Pri-Pr,t-Bu;X=H,CH3,OCH3,OH,F):A Surprising Shortcom

18、ing of Density,t-Bu;X=H,CH3,OCH3,OH,F):A Surprising Shortcoming of Density Functional Theory.Functional Theory.Journal of Physical Chemistry A(2005),109(33),7558-7566.Evolution of the Zhao FunctionalsMPW1B95MPW1B95&MPWB1KMPWB1K J.Phys.Chem.A J.Phys.Chem.A 20042004,108108,6908,6908他引他引:17241724BB1KBB

19、1K J.Phys.Chem.A J.Phys.Chem.A 20042004,108108,4786,4786他引他引:764764M05M05 J.Chem.Phys.J.Chem.Phys.20052005,123123,161103,161103他引他引:12611261M05M05-2X-2X J.Chem.Theory J.Chem.Theory ComputComput.2006,2006,2 2,364,364他引他引:38243824PW6B95PW6B95&PWB6KPWB6K J.Phys.Chem.A J.Phys.Chem.A 20052005,109109(25),

20、5656(25),5656他引他引:15791579M06-LM06-L J.Chem.Phys.J.Chem.Phys.2006,2006,125125,194101,194101他引他引:52015201M06-HFM06-HF J.Phys.Chem.A J.Phys.Chem.A 20062006,110110,13126 ,13126 他引他引:13801380M06M06&M06-2XM06-2X TheorTheor.Chem.Acc.Chem.Acc.20082008,120120,215,215他引他引:2645926459M08-HXM08-HX&M08-SOM08-SO

21、J.Chem.Theory J.Chem.Theory ComputComput.20082008,4 4,1849,1849他引他引:10701070SOGGA SOGGA J.Chem.Phys.J.Chem.Phys.20082008,128128,184109,184109他引他引:336336W20 W20 Phys.Rev.B Phys.Rev.B 20212021,103103,045130,045130他引他引:2 2FunctionalConstraintsTraining SetsUEGSCorFTCBHNCTMM06-LM06M06-2XM06-HFUEG:uniform

22、 electron gas limitUEG:uniform electron gas limitSCorFSCorF:self-correlation free:self-correlation freeTC:main-group thermochemistry TC:main-group thermochemistry BH:barrier heights BH:barrier heights NC:noncovalent interactions NC:noncovalent interactions TM:transition metal chemistryTM:transition

23、metal chemistryM06-Class Density FunctionalsZhao,Y.Zhao,Y.,Truhlar,D.G.Theoretical Chemistry Accounts 20082008,120,1851.Cited 2645926459Zhao,Y.Zhao,Y.,Truhlar,D.G.Acc.Chem.Res.2008,2008,41,157.Cited 70307030-4-3-2-1012BLYPB3LYPPBEB98PBEhTPSShBMKM06-LM06BDE(kcal/mol)BDE=BDE(1)-BDE(2)Best estimate:-3.

24、4 kcal/molGrubbs Catalysts for Olefin MetathesisZhao,Y.;Truhlar,D.G.Attractive noncovalent interactions in the mechanism of Grubbs second-generation Ru catalysts for olefin metathesis.Org.Lett.20072007,9,1967Grubbs CatalystsJ.Am.Chem.Soc.,134,7861(2012);135,5848(2013);137,5782(2015)Organometallics,3

25、4,2858(2015）Nature Energy,2,17008(2017)Robert Grubbs 2005 Nobel Prize WinnerApplications of M06SoftwareThe M06-class functionals have been implemented in:The M06-class functionals have been implemented in:Materials StudioMaterials Studio ADF&BANDADF&BAND GAMESSGAMESS GaussianGaussian JaguarJaguar MO

26、LCASMOLCAS NWChemNWChem Q-Q-ChemChem Spartan 2008Spartan 2008 VASPVASPM06系列理論方法在全世界的化學物理界和材料模擬界都得到了廣泛的應用,M06論文單篇引用超過26000次，有11位諾獎獲得者采用了M06泛函進行理論計算。o56篇Scienceo29篇Natureo65篇Nature Chemistryo24篇Nature Catalysiso18篇Nature Synthesiso7篇Nature Materialso4篇Nature Technologyo4篇Nature EnergyM06密度泛函方法的應用Perde

27、ws Science PaperPerdew et al.Density functional theory is straying from straying from the path toward the exact functional,ScienceScience.20172017,355,49“The M06 suite of functionals is capable of providing accurate electron densities,gradients,and Laplacians using the aug-cc-pV5Z basis set,and thus

28、 it is suitable for a wide range of applications in chemistry and physics.”Wang Y.Truhlar DGTruhlar DG,He,X.He,X.et al.How Well Can the M06 Suite of Functionals Describe the Electron Densities of Ne,Ne6+,and Ne8+?,JCTCJCTC 2018 2018,13,6068W20(Wuhan 2020)均勻電子氣(Uniform Electron Gas,UEG)Xie,Q-X;Wu,J;Z

29、hao,Y.Accurate correlation energy functional for uniform electron gas from an interpolation ansatz without fitting parameters.Phys.Rev.B 20212021,103,045130LSDAUEGxcxc,(,)dEerUEG21/3xFs333(9/4)()(3)444ekr 00011(,)()ln()()=()ln()()()ln()().(0)ncsnsnsnsssse rarbrarbr arbrHDL(High Density Limit)LDL(Low

30、 Density Limit)021exp3/221/23()()(,)(,)()xsncsssnsnsssfcfcffe rerrrrrrUEGUEGUEGxcxceeeW20(Wuhan 2020)Xie,Q-X;Wu,J;Zhao,Y.Accurate correlation energy functional for uniform electron gas from an interpolation ansatz without fitting parameters.Phys.Rev.B 20212021,103,04513000011(,)()ln()()=()ln()()()ln

31、()().(0)ncsnsnsnsssse rarbrarbr arbrHDL(High Density Limit)LDL(Low Density Limit)021exp3/221/23()()(,)(,)()xsncsssnsnsssfcfcffe rerrrrrrW2003/22()(,)(,)(,)(,)ln 1(,)2ssscssssaD rE rF re rG rrrr200002/(/100)2/00()1(,)2 1()2sbarbaxsfcD reeea2(/100)102 1(,)()srsefE ra 200002/(/100)2/20()1(,)2 1()2sbarb

32、assfcF reeea211(/100)5/41(,)()ln 1()1 10sssrssrG rabrerXie,Q-X;Wu,J;Zhao,Y.Accurate correlation energy functional for uniform electron gas from an interpolation ansatz without fitting parameters.Phys.Rev.B 20212021,103,045130W20不依賴任何經驗擬合參數以2013年的QMC計算結果作為評估標準，W20泛函優于當前流行的一些UEG泛函W20與QMC的計算誤差在0.01eV的范

33、圍內在低密度極限下，W20方法能夠更好地擬合UEG的關聯能Xie,Q-X;Wu,J;Zhao,Y.Accurate correlation energy functional for uniform electron gas from an interpolation ansatz without fitting parameters.Phys.Rev.B 20212021,103,04513024WMS(Wuhan-Minnesota-Scaling)Phys.Chem.Chem.Phys.2018,20,27235-27384.WIRES Computational Molecular S

34、cience 2020,10,e1474.Doubly Hybrid DFTJ.Phys.Chem.A,2004,108,4786Phys.Chem.Chem.Phys.,2005,7,43WIRES Computational Molecular Science 2020,10,e1474.Jacobs Ladder of Density Functional ApproximationsEarthHartree WorldLSDA(r)W20GGA(r)Meta-GGA(r)or Hybrid FunctionalsHF ExDoubly Hybrid Functionals virtua

35、l orbitalsChemical AccuracyHeavenSOGGAM06-LBB1K,MPW1B95,PW6B95,M05-class,M06,M06-2X,M06-HF,M08-classMC3BB,MC3MPW,MC MCG3-TSJacob left Beersheba and set out for Harran.When he reached a certain place,he stopped for the night because the sun had set.Taking one of the stones there,he put it under his h

36、ead and lay down to sleep.He had a dream in which he saw a stairway resting on the earth,with its top reaching to heaven,and the angels of God were ascending and descending on it.Genesis 28:10-12基于量子計算的量子化學算法 研究非變分的量子算法研究非幺正量子算子在量子計算機上的實現將非幺正量子算法算法推廣至激發態的計算 研究并改進變分類量子算法設計更精簡更高效的量子線路推廣變分量子算法至任意激發態的計算

37、提升變分量子算法的計算精度J.Chem.Theory Comput.,2022,18(6),3737-3746J.Chem.Theory Comput.,2022,18(12),75867602Inter.J.of Quantum Chem.,2022,122(24),e2700128工作成果高精度電化學數據庫J.Phys.Chem.C,2019,123,20737-20747.International Journal of Quantum Chemistry,2022,122:e26886M08-HXM08-HX泛函是計算精度最優的泛函是計算精度最優的DFTDFT方法，且經計算溶劑的電化學

38、性能發現氟取代有助于提高溶劑的方法，且經計算溶劑的電化學性能發現氟取代有助于提高溶劑的氧化還原電位及氧化還原電位及HOMO/LUMOHOMO/LUMO值，這為篩選合適的鋰金屬電池電解液氟化溶劑提供了理論指導。值，這為篩選合適的鋰金屬電池電解液氟化溶劑提供了理論指導。HOMO/LUMO gap工作成果多硫化鋰錨固和催化轉化材料理論研究金屬酞菁摻雜改性異質結改性抑制形變篩選摻雜改性Ti,Mn,Fe,Co,Ni,CuTM=Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn摻雜改性Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Cd硼烯六方相氮化硼硒化物摻雜改性增強吸附和催化Appl.

39、Surf.Sci.,2021,558,149928.Appl.Surf.Sci.,2020,534,147575.J.Colloid Interface Sci.,2022,616,886-894.Appl.Surf.Sci.,2021,570.工作成果實驗結合理論計算構筑高性能鋰硫電池材料 ACS Appl.Mater.Interfaces,2020,12,9181-9189.Chem.Eng.J.2022.439.135679NixCo3-xS4/NC 工作成果實驗結合理論計算構筑高性能鋰硫電池材料Theoretical CalculationsExperimentHigh-Perform

40、ance BatteryM-NCMXeneNano Res.,2020,13,2299-2307.Adv.Mater.,2023,35,2302418.工作成果合金修飾層設計與界面反應動力學模擬33多尺度界面反應動力學模擬與實驗結合，發現了合金層局域化電多尺度界面反應動力學模擬與實驗結合，發現了合金層局域化電子、表面活性與鋰離子沉積行為的相互聯系。子、表面活性與鋰離子沉積行為的相互聯系。Nano Energy 2021,88,106237Adv.Sci.2022,9,2105656Phys.Chem.Chem.Phys.2022,24,4751梯度合金層梯度合金層均勻沉積均勻沉積h工作成果高性

41、能電解質設計及其性能研究研究工作：溶劑數據庫構建及電解液組分設計研究工作：溶劑數據庫構建及電解液組分設計通過通過密度泛函方法計算篩選出一種新型、熱力學穩定性優異的氟化溶劑。密度泛函方法計算篩選出一種新型、熱力學穩定性優異的氟化溶劑。實驗結果顯示，使用氟化電解液組裝的全電池具有優異的循環穩定性和實驗結果顯示，使用氟化電解液組裝的全電池具有優異的循環穩定性和高的庫倫效率。高的庫倫效率。研究背景：鋰金屬負極界面副反應引起系列的穩研究背景：鋰金屬負極界面副反應引起系列的穩 定性問題定性問題關鍵突破點：設計抗氧化還原、高兼容性的高壓電解質體關鍵突破點：設計抗氧化還原、高兼容性的高壓電解質體系系Energy Stor.Mater.2022,51,317Energy Stor.Mater.2023,57,249Int.J.Quantum Chem.2022,122,e26886 新材料新材料小結小結o 發表 了250+篇論文，被引用65000余次,10篇論文單篇引用超1000次，h-index:73。o 20篇論文被ISI Web of Science 評為Highly Cited Papers。36