A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements...
-
Upload
rylan-keathley -
Category
Documents
-
view
247 -
download
0
Transcript of A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements...
![Page 1: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/1.jpg)
A New Set of Accurate Multi-level
Methods Including Parameterization for Heavy Elements
演講者:孫翊倫 (Yi-Lun Sun)指導教授:胡維平 (Wei-Ping Hu)
中華民國 101 年 6 月 11 日
![Page 2: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/2.jpg)
Content• Chapter 1
A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements
• Chapter 2 & 3
Theoretical Prediction of A New Class of Xenon Containing Molecules and Anions
• Chapter 4
Theoretical Study on the Excited State Dynamics of Phenol Chromophores
Chapter 5
Theoretical Prediction of A New Type Xe Polymer
2
![Page 3: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/3.jpg)
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
3
●●
![Page 4: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/4.jpg)
• Example:MP2/aug-cc-pVDZQCISD(T)/aug-cc-pVTZ
• Deficiencies:1. Low accuracy2. Cost expensive
4
Single Level Methods
![Page 5: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/5.jpg)
5
Error of the reaction energy :CH4 + Cl2 → CH3Cl + HClMP2/aug-cc-pVDZ : 8.1 kcal/molQCISD(T)/aug-cc-pVTZ : 1.9 kcal/mol
CH4 → C + 4 H (atomization energy)MP2/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
![Page 6: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/6.jpg)
6
Cost :
MP2/aug-cc-pVDZTime : 1 unit
QCISD(T)/aug-cc-pVTZTime : 288 units~ couple hours
Single Level Methods
![Page 7: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/7.jpg)
Popular Multi-level Methods: G1, G2, G3, G4
Multi-level Methods with Scaled Energies: (Multi-coefficient Method)
MCG3, G3S, G3X , MLSEn+d
Multi-level Methods
7
![Page 8: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/8.jpg)
G3 theory• 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
8
![Page 9: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/9.jpg)
MLSEn+d Method
E(MLSEn+d) =
CHF × E(HF/cc-pV(D+d)Z) +
CHF × [E(HF/cc-pV(T+d)Z )– E(HF/cc-pV(D+d)Z)] +
CE2 × [E2/cc-pV(D+d)Z] +
CE34 × [E(MP4SDQ/cc-pV(D+d)Z) – E(MP2/cc-pV(D+d)Z)] +
CQCI × [E(QCISD(T)/cc-pV(D+d)Z) – E(MP4SDQ/cc-pV(D+d)Z)] +
CB × γE2 × [E2/cc-pV(T+d)Z – E2/cc-pV(D+d)Z] +
C+ × [E2/aug-cc-pV(D+d)Z – E2/cc-pV(D+d)Z] + ESO
Chem. Phys. Lett. 2005, 412, 430-433
9
![Page 10: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/10.jpg)
Density functional theory (DFT)
• To obtain energies of molecules and their physical properties without solving wave functions.
• Common functionals:
B3LYP 、 MPW1B95 、 MPW1PW91 、 TPSS1KCIS 、 B1B95 、 M06-2X
10
![Page 11: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/11.jpg)
The MLSE-DFT Method
E(MLSE-DFT) = CWF { E(HF/cc-pV(D+d)Z) +
CHF [E(HF/cc-pV(T+d)Z )– E(HF/cc-pV(D+d)Z)] +
CE2 [E2/cc-pV(D+d)Z] +
CE34 [E(MP4SDQ/cc-pV(D+d)Z) – E(MP2/cc-pV(D+d)Z)] +
CQCI [E(QCISD(T)/cc-pV(D+d)Z) – E(MP4SDQ/cc-pV(D+d)Z)] +
CB [E2/cc-pV(T+d)Z – E2/cc-pV(D+d)Z] +
CHF+ [E(HF/aug-cc-pV(D+d)Z) – E(HF/cc-pV(D+d)Z]) +
CE2+ [E2/aug-cc-pV(D+d)Z – E2/cc-pV(D+d)Z] } +
(1 - CWF ) { E(DFTX/cc-pV(D+d)Z) +
CB1 [E(DFTX/cc-pV(T+d)Z – DFTX/cc-pV(D+d)Z] } + ESO Chem. Phys. Lett. 2007, 442, 220.
11
![Page 12: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/12.jpg)
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] } .
12
Chem. Phys. Lett. 2009, 475, 141.
![Page 13: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/13.jpg)
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.
Train sets and Test sets
NHTBH38 Database. 38 transition state barrier heights for non-hydrogentransfer(NHT) reactions.
13
![Page 14: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/14.jpg)
Accuracy
14
AE(109)
IP(13)
EA(13)
HTBH(38)
NHTBH(38)
Overall MUE
MLSE(C1)-M06-2X 0.62 0.55 0.63 0.47 0.43 0.56
MLSE(C2)-M06-2X 0.65 0.60 0.69 0.50 0.44 0.59
MLSE(C3)-B3LYP 0.62 0.68 0.82 0.45 0.68 0.62
MLSE-TS 0.62 - - 0.55 0.69 0.61
QCISD(T) /aug-cc-pVTZ
10.90 2.05 1.94 0.60 0.73 6.11
![Page 15: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/15.jpg)
Computational Cost
15
Cost MUE
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
![Page 16: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/16.jpg)
16
CH4 + Cl2 → CH3Cl + HCl
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)
MP2/aug-cc-pVDZ : 25.6 kcal/molQCISD(T)/aug-cc-pVTZ : 6.0 kcal/molMLSE(C1)-M06-2X : 0.13 kcal/mol
Accuracy
![Page 17: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/17.jpg)
For Heavy Elements?
17
CH4 + I2 → CH3I + HIQCISD(T)/aug-cc-pVTZ : 4.7 kcal/molMLSE(C1)-M06-2X : 2.7 kcal/mol
I2 → 2 IQCISD(T)/aug-cc-pVTZ : 5.4 kcal/molMLSE(C1)-M06-2X : 4.3 kcal/mol
![Page 18: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/18.jpg)
New Database
18
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
![Page 19: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/19.jpg)
MLSE(HA-1)
HF MP2 MP4 QCISD(T) MPW1PW91
pdz ●
apdz ● ●
ptz ●
aptz ● ●
19
● ● ●
● ● ●
● ●
●
![Page 20: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/20.jpg)
20
MLSE(HA-1)
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).
![Page 21: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/21.jpg)
MLSE(HA-2)
HF MP2 MP4 QCISD(T) MPW1PW91
pdz ● ● ● ●
apdz ● ● ● ●
ptz ● ● ●
aptz ● ●
21
●
●
●
![Page 22: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/22.jpg)
New Database
22
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
![Page 23: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/23.jpg)
Accuracy
23
(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
![Page 24: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/24.jpg)
Computational Cost
24
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
![Page 25: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/25.jpg)
Results
25
CH4 + I2 → CH3I + HIQCISD(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 IQCISD(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
![Page 26: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/26.jpg)
Results
26
CH3I + Cl- → CH3Cl + I-, Erxn = 12.66 kcal/molQCISD(T)/aug-cc-pVTZ : 2.01 kcal/molMLSE(C1)-M06-2X : 2.22 kcal/molMLSE(HA-1) : 0.03 kcal/molMLSE(HA-2) : 0.58 kcal/mol
CH3Br + Cl- → CH3Cl + Br- , Erxn = 7.90 kcal/molQCISD(T)/aug-cc-pVTZ : 1.75 kcal/molMLSE(C1)-M06-2X : 0.91 kcal/molMLSE(HA-1) : 0.28 kcal/molMLSE(HA-2) : 0.75 kcal/mol
![Page 27: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/27.jpg)
Concluding Remarks
• 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.
27
![Page 28: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/28.jpg)
Concluding Remarks
• We recommend MLSE(HA-1) method for the heavy halogens containing systems.
• The simplified, but reasonably accurate, MLSE(HA-2) method is an economical alternative for larger systems.
28
![Page 29: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/29.jpg)
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
29
![Page 30: A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements 演講者:孫翊倫 (Yi-Lun Sun) 指導教授:胡維平 (Wei-Ping Hu) 中華民國 101 年](https://reader033.fdocuments.us/reader033/viewer/2022061517/56649d835503460f94a690d7/html5/thumbnails/30.jpg)
Thanks for your attention
30