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(Cn)-DFT for Thermochemical Kinetics

• Chapter 2A 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

2博士論文口試

Content• Chapter 4

Theoretical Prediction of A New Class of Xenon Containing Molecules and Anions NXeOnFm

• Chapter 5Theoretical Study on the Excited State Dynamics of Phenol Chromophores

Chapter 6Theoretical Prediction of A New Type Xe Polymer

博士論文口試

• Chapter 2A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements

3

Theoretical Study on the Excited State Dynamics of

Phenol Chromophores

Tyrosine

博士論文口試

Tyrosine, one of the 22 amino acids that are used by cells to synthesize proteins.

5

Fluorescence?

博士論文口試

The so-called photostability prevents the undesired photochemical reactions for these molecules upon the irradiation with ultraviolet photons.

6

PES of phenol

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

7

2-hydroxybenzoic acid

博士論文口試 8

2-HBA 3-HBA

4-HBA

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 9

active space

博士論文口試

CAS(12,12)/6-31+G**12 electrons and 12 orbitals (6, 4*, and 2*)

10

3-HBA and 4-HBA

博士論文口試 11

3-HBA and 4-HBA

博士論文口試 12

3-HBA

4-HBA

2-HBA

博士論文口試 13

2-HBA-1

博士論文口試

CAS(12,12)/6-31+G**

14

2-HBA-3

博士論文口試CAS(12,12)/6-31+G**

15

HAP, MOBA

博士論文口試 16

2-hydroxyacetophenone(2-HAP)

2-methoxybenzoic acid(2-MOBA)

HAP, MOBA

博士論文口試 17

2-HAP-1

博士論文口試 18

2-HAP-2

博士論文口試 19

2-MOBA-1

博士論文口試 20

Conclusions• Recent theoretical

calculations suggested that the low fluorescence quantum yield for phenol was due to dissociation from an excited electronic state potential energy surface.

博士論文口試 21

Sobolewski, A. L.; Domcke, W. Chem. Phys. 2000, 259, 181.

2-hydroxybenzoic acid

博士論文口試 22

2-HBA 3-HBA

4-HBA

Conclusions• For various conformers of HBA

and HAP without intramolecular 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 23

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 24

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 25

A New Set of Accurate Multi-level Methods

Including Parameterization for Heavy Elements

　 　 　 　 　　 　 　 　 　　 　 　 　 　　 　 　 　 　　 　 　 　 　

　 　 　 　 　

　　　　　

SchrödingerEquation 　

Electron correlation →

Basis set Type

3-21G

6-31+G**

aug-cc-pVDZ

aug-cc-pVTZ

aug-cc-pVQZ

HF MP2 MP3 MP4 QCISD(T) … Full CI

… … … … … … …

∞

Quantum Chemical Calculations

27

●●

博士論文口試

• Example:MP2/aug-cc-pVDZQCISD(T)/aug-cc-pVTZ

• Deficiencies:1. Low accuracy2. Cost expensive

28

Single Level Methods

博士論文口試

29

Error of the reaction energy ：CH4 + Cl2 → CH3Cl + HCl, Erxn = -23.1 kcal/molMP2/aug-cc-pVDZ ： 8.1 kcal/molQCISD(T)/aug-cc-pVTZ ： 1.9 kcal/mol

CH4 → C + 4 H (atomization energy) , Erxn = 420.1 kcal/molMP2/aug-cc-pVDZ ： 25.6 kcal/molQCISD(T)/aug-cc-pVTZ ： 6.0 kcal/mol

MP2/aug-cc-pVDZ > 5 kcal/molQCISD(T)/aug-cc-pVTZ > 1 kcal/mol

Single Level Methods

博士論文口試

30

Cost ：MP2/aug-cc-pVDZTime ： 1 unit

QCISD(T)/aug-cc-pVTZTime ： 288 units~ couple hours

Single Level Methods

博士論文口試

Popular Multi-level Methods: G1, G2, G3, G4

Multi-level Methods with Scaled Energies: (Multi-coefficient Method)

MCG3, G3S, G3SX , MLSEn+d

Multi-level Methods

31博士論文口試

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

Journal of Chemical Physics, 1998, 109, 7764-7776 32

C1 C2 C3 C4

博士論文口試

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] } .

33

Chem. Phys. Lett. 2009, 475, 141. 博士論文口試

Database

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.

Training sets

NHTBH38 Database. 38 transition state barrier heights for non-hydrogentransfer(NHT) reactions.

34博士論文口試

MLSE(C1)-M062X

HF MP2 MP4 QCISD(T) M06-2X

pdz ● ●

apdz ● ●

ptz ●

●

35

● ● ●

●

● ●

●

博士論文口試

aptz

Computational Cost

36

Cost MUE (kcal/mol)

MP2/aug-cc-pVDZ 1 15.1

MLSE(C1)-M06-2X 70 0.56

MLSE(C2)-M06-2X 50 0.59

MLSE(C3)-B3LYP 25 0.62

MLSE-TS 25 0.61

QCISD(T)/aug-cc-pVTZ 288 6.11

M06-2X/aug-cc-pVTZ 16 1.89

博士論文口試

37

CH4 + Cl2 → CH3Cl + HCl , Erxn = -23.1 kcal/mol

MP2/aug-cc-pVDZ ： 8.1 kcal/molQCISD(T)/aug-cc-pVTZ ： 1.9 kcal/molMLSE(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/molQCISD(T)/aug-cc-pVTZ ： 6.0 kcal/molMLSE(C1)-M06-2X ： 0.13 kcal/mol

Accuracy

博士論文口試

MLSE(Cn)-DFT

博士論文口試 38

For Heavy Elements?

39

CH4 + I2 → CH3I + HI , Erxn= 13.1 kcal/molQCISD(T)/aug-cc-pVTZ ： 4.7 kcal/molMLSE(C1)-M06-2X ： 2.7 kcal/mol

I2 → 2 I , Erxn= 35.9 kcal/molQCISD(T)/aug-cc-pVTZ ： 5.4 kcal/molMLSE(C1)-M06-2X ： 4.3 kcal/mol

博士論文口試

New Database

40

unit:kcal/mol AE AE IP

I2 35.87 HBr 90.51 I 241.01

HI 73.79 NOBr 181.64 Br 272.43

IBr 42.27 CH3I 369.12 EA

ICl 50.19 CH3Br 380.94 I 70.54

Br2 45.90 C2H5I 662.69 Br 77.60

博士論文口試

MLSE(C1)-M062X

博士論文口試 41

(unit : kcal/mol) MUE(225)

HHAE(10)

HHIP(2)

HHEA(2)

MLSE(C1)-M062X(Eso) 0.66 1.84 1.22 2.21

MLSE(C1)-M062X-HA 0.66 1.66 1.21 2.30

42

SCS-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] +

The different scaling factors were used to the same spin and opposite spin perturbational terms (MP2).

博士論文口試

MLSE(HA-1)

HF MP2 MP4 QCISD(T) MPW1PW91

pdz ●

apdz ● ●

ptz ●

aptz ● ●

43

● ● ●

● ● ●

● ●

●

博士論文口試

MLSE(HA-2)

HF MP2 MP4 QCISD(T) MPW1PW91

pdz ● ● ● ●

apdz ● ● ● ●

ptz ● ● ●

aptz ● ●

44

●

●

●

博士論文口試

New Database

45

unit : kcal/mol AE AE IP

I2 35.87 HBr 90.51 I 241.01

HI 73.79 NOBr 181.64 Br 272.43

IBr 42.27 CH3I 369.12 EA

ICl 50.19 CH3Br 380.94 I 70.54

Br2 45.90 C2H5I 662.69 Br 77.60

博士論文口試

Accuracy

46

(unit : kcal/mol) MUE(225)

HHAE(10)

HHIP(2)

HHEA(2)

MLSE(C1)-M062X(Eso) 0.66 1.84 1.22 2.21

MLSE(C1)-M062X-HA 0.66 1.66 1.21 2.30

MLSE(HA-1) 0.58 0.87 0.49 1.07

MLSE(HA-2) 0.64 0.98 0.48 1.04

博士論文口試

Computational Cost

47

(unit : kcal/mol) Cost MUE(211)

MUE(225)

HHAE(10)

MLSE(C1)-M062X 100% 0.56 0.66 1.66

MLSE(HA-1) 162% 0.56 0.58 0.87

MLSE(HA-2) 104% 0.62 0.64 0.98

博士論文口試

Results

48

CH4 + I2 → CH3I + HI , Erxn= 13.1 kcal/molQCISD(T)/aug-cc-pVTZ ： 4.7 kcal/molMLSE(C1)-M06-2X ： 2.7 kcal/molMLSE(HA-1) ： 0.5 kcal/molMLSE(HA-2) ： 1.0 kcal/mol

I2 → 2 I , Erxn= 35.9 kcal/molQCISD(T)/aug-cc-pVTZ ： 5.4 kcal/molMLSE(C1)-M06-2X ： 4.3 kcal/molMLSE(HA-1) ： 0.7 kcal/molMLSE(HA-2) ： 0.6 kcal/mol博士論文口試

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 49

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.

50博士論文口試

Acknowledgement• Prof. Wei-Ping Hu• Our group members.

(Tsung-Hui Li, Jien-Lian Chen et al.)• Department of Chemistry & Biochemistry,

National Chung Cheng University• National Science Council• National Center for High-Performance

Computing

51博士論文口試

Thanks for your attention

52博士論文口試