1 / 52

國立中正大學 化學暨生物化學研究所 博士論文口試 孫翊倫 (Yi-Lun Sun) 指導教授：胡維平 (Wei-Ping Hu) 中華民國 101 年 7 月 10 日

國立中正大學 化學暨生物化學研究所 博士論文口試 孫翊倫 (Yi-Lun Sun) 指導教授：胡維平 (Wei-Ping Hu) 中華民國 101 年 7 月 10 日. Content. Chapter 1 Accurate Multi-Coefficient Electronic Structure Methods MLSE( C n )-DFT for Thermochemical Kinetics Chapter 2

altessa
Download Presentation

國立中正大學 化學暨生物化學研究所 博士論文口試 孫翊倫 (Yi-Lun Sun) 指導教授：胡維平 (Wei-Ping Hu) 中華民國 101 年 7 月 10 日

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  1. 國立中正大學 化學暨生物化學研究所 博士論文口試 孫翊倫(Yi-Lun Sun) 指導教授：胡維平 (Wei-Ping Hu) 中華民國101年7月10日

  2. Content • Chapter 1Accurate Multi-Coefficient Electronic Structure Methods MLSE(Cn)-DFT for Thermochemical Kinetics • Chapter 2 A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements • Chapter 3 Theoretical Prediction of Stable Noble-Gas Anions XeNO2- and XeNO3- with very Short Xenon-Nitrogen Bond Lengths 博士論文口試

  3. Content • Chapter 4 Theoretical Prediction of A New Class of Xenon Containing Molecules and Anions NXeOnFm • Chapter 5 Theoretical Study on the Excited State Dynamics of Phenol Chromophores • Chapter 6 Theoretical Prediction of A New Type Xe Polymer • Chapter 2 A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 博士論文口試

  4. Theoretical Study on the Excited State Dynamics of Phenol Chromophores

  5. Tyrosine Tyrosine, one of the 22 amino acids that are used by cells to synthesize proteins. 博士論文口試

  6. Fluorescence? The so-called photostability prevents the undesired photochemical reactions for these molecules upon the irradiation with ultraviolet photons. 博士論文口試

  7. PES of phenol Sobolewski, A. L.; Domcke, W. Chem. Phys.2000, 259, 181. 博士論文口試

  8. 2-hydroxybenzoicacid 3-HBA 2-HBA 4-HBA 博士論文口試

  9. methods • Geometry:B3LYP/6-311+G** • PES: TD B3LYP/6-311+G**CAS/6-31+G** • Program:Gaussian 03/09Molpro 2010 博士論文口試

  10. active space CAS(12,12)/6-31+G**12  electrons and 12 orbitals (6p, 4p*, and 2*) 博士論文口試

  11. 3-HBA and 4-HBA 博士論文口試

  12. 3-HBA and 4-HBA 3-HBA 4-HBA 博士論文口試

  13. 2-HBA 博士論文口試

  14. 2-HBA-1 CAS(12,12)/6-31+G** 博士論文口試

  15. 2-HBA-3 CAS(12,12)/6-31+G** 博士論文口試

  16. HAP, MOBA 2-methoxybenzoic acid(2-MOBA) 2-hydroxyacetophenone(2-HAP) 博士論文口試

  17. HAP, MOBA 博士論文口試

  18. 2-HAP-1 博士論文口試

  19. 2-HAP-2 博士論文口試

  20. 2-MOBA-1 博士論文口試

  21. Conclusions • Recent theoretical calculationssuggested that the low fluorescence quantum yield for phenol was due to dissociation from an excited electronic state potential energy surface. Sobolewski, A. L.; Domcke, W. Chem. Phys.2000, 259, 181. 博士論文口試

  22. 2-hydroxybenzoicacid 3-HBA 2-HBA 4-HBA 博士論文口試

  23. Conclusions • For various conformers of HBA and HAP withoutintramolecular hydrogen bonding, the second excited state is a repulsive state. It crosses 2A' at short O-H bond distance and crosses 1A' at large O-H bond distance. • Hydrogen atom elimination can occur easily on this repulsive potential energy surface. 博士論文口試

  24. Conclusions • For all the MOBA, the second excited state is a repulsive state. It crosses 2A' at short O-C bond distance and crosses 1A' at large O-C bond distance. • CH3 group elimination can occur easily on this repulsive potential energy surface. 博士論文口試

  25. Conclusions • For conformers of 2-HBA and 2-HAP with intramolecular hydrogen bonding, the formation of intramolecular hydrogen bonding reduces the ground state (1A') energy significantly at large O-H distances due to the formation of zwitterionic species and avoids the intersecting with the 1A" state. • No H atom elimination analogous to that of phenol was observed 博士論文口試

  26. A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements

  27. Quantum Chemical Calculations Electron correlation → HF MP2 MP3 MP4 QCISD(T) … Full CI Basis set Type 3-21G 6-31+G** aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ ● ● … … … … … … … ∞ 博士論文口試

  28. Single Level Methods • Example: • MP2/aug-cc-pVDZ • QCISD(T)/aug-cc-pVTZ • Deficiencies: • Low accuracy • Cost expensive 博士論文口試

  29. Single Level Methods Error of the reaction energy： CH4 + Cl2→ CH3Cl + HCl, Erxn = -23.1 kcal/mol MP2/aug-cc-pVDZ：8.1 kcal/mol QCISD(T)/aug-cc-pVTZ：1.9 kcal/mol CH4→ C + 4 H (atomization energy) , Erxn = 420.1 kcal/mol MP2/aug-cc-pVDZ：25.6 kcal/mol QCISD(T)/aug-cc-pVTZ：6.0 kcal/mol MP2/aug-cc-pVDZ > 5 kcal/mol QCISD(T)/aug-cc-pVTZ > 1 kcal/mol 博士論文口試

  30. Single Level Methods Cost： MP2/aug-cc-pVDZ Time：1 unit QCISD(T)/aug-cc-pVTZ Time：288 units ~ couple hours 博士論文口試

  31. Multi-level Methods Popular Multi-level Methods: G1, G2, G3, G4 Multi-level Methods with Scaled Energies: (Multi-coefficient Method) MCG3, G3S, G3SX , MLSEn+d 博士論文口試

  32. G3 & G3S • Geometry:MP2(full)/6-31G(d) • Ebase: MP4/6-31G(d) • ΔE+ : MP4/6-31+G(d) -Ebase • Δ E2df,p : MP4/6-31G(2df,p) – Ebase • Δ EQCI : QCISD(T)/6-31G(d) – Ebase • Δ EG3Large : MP2(full)/G3Large – [ MP2/6-31G(2df,p) +MP2/6-31+G(d) – MP2/6-31G(d) ] • Δ EHLC : – Anβ – B(nα –nβ) E(G3)= Ebase+ ΔE+ + ΔE2df,p + ΔEQCI + ΔEG3Large +ΔEHLC + EZPE C1 C2 C3 C4 Journal of Chemical Physics, 1998, 109, 7764-7776 博士論文口試

  33. The MLSE(C1)-DFT Method • E(MLSE(C1)-DFT) = CWF { E(HF/pdz) +CE2 [E2/pdz] +CE34SDQ [E(MP4SDQ/pdz) – E(MP2/pdz)] +CQCID [E(QCISD/pdz) – E(MP4SDQ/pdz)] + CQCI [E(QCISD(T)/pdz) – E(QCISD/pdz)] +CB1E2 [E2/ptz – E2/pdz] + CHF+ [E(HF/apdz) – E(HF/pdz]) +CE2+ [E2/apdz – E2/pdz] +CB2E2 [E2/aptz – E2/apdz] +CB1E34 [E(MP4D/ptz) – E(MP4D/pdz)] } + (1 - CWF ) { E(DFTX/pdz) + CDFT+ [E(DFTX/apdz – DFTX/pdz] } . Chem. Phys. Lett. 2009,475, 141. 博士論文口試

  34. Database Training sets MGAE109 Database. 109 atomization energies (AEs). IP13 and EA13 Database. 13 IPs and 13 EAs HTBH38 Database. 38 transition state barrier heights for hydrogen transfer (HT) reactions. NHTBH38 Database. 38 transition state barrier heights for non-hydrogentransfer (NHT) reactions. 博士論文口試

  35. MLSE(C1)-M062X aptz 博士論文口試

  36. Computational Cost 博士論文口試

  37. Accuracy CH4 + Cl2→ CH3Cl + HCl , Erxn = -23.1 kcal/mol MP2/aug-cc-pVDZ：8.1 kcal/mol QCISD(T)/aug-cc-pVTZ：1.9 kcal/mol MLSE(C1)-M06-2X： 1.0 kcal/mol CH4→ C + 4 H (atomization energy) , Erxn = 420.1 kcal/mol MP2/aug-cc-pVDZ：25.6 kcal/mol QCISD(T)/aug-cc-pVTZ：6.0 kcal/mol MLSE(C1)-M06-2X： 0.13 kcal/mol 博士論文口試

  38. MLSE(Cn)-DFT 博士論文口試

  39. For Heavy Elements? CH4 + I2→ CH3I + HI , Erxn= 13.1 kcal/mol QCISD(T)/aug-cc-pVTZ：4.7 kcal/mol MLSE(C1)-M06-2X ：2.7 kcal/mol I2→ 2 I, Erxn= 35.9 kcal/mol QCISD(T)/aug-cc-pVTZ：5.4 kcal/mol MLSE(C1)-M06-2X ：4.3 kcal/mol 博士論文口試

  40. New Database 博士論文口試

  41. MLSE(C1)-M062X 博士論文口試

  42. SCS-MP2 The different scaling factors were used to the same spin and opposite spin perturbational terms (MP2). CE2S[(E2aa+E2bb)/pdz] + CE2O[(E2ab)/pdz] + CE2+S[(E2aa+E2bb)/apdz] + CE2+O[(E2ab)/apdz] + CB1E2S[(E2aa+E2bb)/ptz] + CB1E2O[(E2ab)/ptz] + CB2E2S[(E2aa+E2bb)/aptz] + CB2E2O[(E2ab)/aptz] + 博士論文口試

  43. MLSE(HA-1) 博士論文口試

  44. MLSE(HA-2) ● ● ● 博士論文口試

  45. New Database 博士論文口試

  46. Accuracy 博士論文口試

  47. Computational Cost 博士論文口試

  48. Results CH4 + I2→ CH3I + HI , Erxn= 13.1 kcal/mol QCISD(T)/aug-cc-pVTZ：4.7 kcal/mol MLSE(C1)-M06-2X ：2.7 kcal/mol MLSE(HA-1)：0.5 kcal/mol MLSE(HA-2)：1.0 kcal/mol I2→ 2 I , Erxn= 35.9 kcal/mol QCISD(T)/aug-cc-pVTZ：5.4 kcal/mol MLSE(C1)-M06-2X ：4.3 kcal/mol MLSE(HA-1)：0.7 kcal/mol MLSE(HA-2)：0.6 kcal/mol 博士論文口試

  49. Conclusions • The MLSE(C1)-M06-2X method provided the lowest overall MUE of 0.56 kcal/mol on the training set. • Both MLSE(C1)-M06-2X (Eso) and MLSE(C1)-M06-2X-HA methods performed unsatisfactorily on the 10 heavy halogen containing atomization energies(>1 kcal/mol). 博士論文口試

  50. Conclusions • MLSE(HA-1) and MLSE(HA-2) performed 0.58 and 0.64 kcal/mol on the MUE(225), with the MUE of HHAE(10) both less than 1 kcal/mol. • MLSE(HA-1) method required 62% cost more than the MLSE(C1)-M06-2X method. But MLSE(HA-2) method only cost 4% more than the MLSE(C1)-M06-2X method. 博士論文口試

More Related