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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. Content. Chapter 1 A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements Chapter 2 & 3 - PowerPoint PPT Presentation
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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
Content• Chapter 1
A New Set of Accurate Multi-level Methods Including Parameterization for Heavy Elements
• Chapter 2 & 3Theoretical Prediction of A New Class of Xenon Containing Molecules and Anions
• Chapter 4Theoretical Study on the Excited State Dynamics of Phenol Chromophores
Chapter 5Theoretical Prediction of A New Type Xe Polymer
2
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
●●
• Example:MP2/aug-cc-pVDZQCISD(T)/aug-cc-pVTZ
• Deficiencies:1. Low accuracy2. Cost expensive
4
Single Level Methods
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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
6
Cost :MP2/aug-cc-pVDZTime : 1 unit
QCISD(T)/aug-cc-pVTZTime : 288 units~ couple hours
Single Level Methods
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
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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
MLSEn+d MethodE(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
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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
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The MLSE-DFT MethodE(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
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.
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
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 0.61QCISD(T) /aug-cc-pVTZ 10.90 2.05 1.94 0.60 0.73 6.11
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
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
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
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
MLSE(HA-1)
HF MP2 MP4 QCISD(T) MPW1PW91
pdz ●
apdz ● ●
ptz ●
aptz ● ●
19
● ● ●
● ● ●
● ●
●
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).
MLSE(HA-2)
HF MP2 MP4 QCISD(T) MPW1PW91
pdz ● ● ● ●
apdz ● ● ● ●
ptz ● ● ●
aptz ● ●
21
●
●
●
New Database
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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
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
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
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
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
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
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
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
Thanks for your attention
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