Development of Large - scale Quantum Mechanical Molecular Dynamics Simulation: Divide - and - conquer Density Functional T ight - binding Approach Yoshifumi Nishimura, 1 Aditya Wibawa Sakti, 2 and Hiromi Nakai 1–4 1 RISE, Waseda Univ., 2 Waseda Univ., 3 JST-CREST, 4 ESICB, Kyoto Univ. 1 The 1st International Workshop on Advanced Methods for Nano Materials Design (2017/07/14, KINTEX, Gyeonggi-do, Korea)
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Development of Large-scale Quantum Mechanical Molecular Dynamics Simulation: Divide-and-conquer Density Functional Tight-binding Approach
The 1st International Workshop on Advanced Methods for Nano Materials Design (2017/07/14, KINTEX, Gyeonggi-do, Korea)
2
Chemical reaction simulation of large systems
Bond formation/cleavage, Electron transfer
QM-MD Classical MD
WFT DFT DFTB MM
Cluster collision[1] Electrolyte decomposition[2]
Carbon nanotube growth[3] Virus[4]
< 100 < 1000 < 1000 ~10000000
[1] H. Nakai, Y. Yamauchi, A. Matsuda, Y. Okada, K. Takeuchi, J. Mol. Struct. (THEOCHEM) 592, 61 (2002).[2] K. Ushirogata, K. Sodeyama, Y. Okuno, Y. Tateyama, J. Am. Chem. Soc. 135, 11967 (2013).[3] A. J. Page, Y. Ohta, S. Irle, K. Morokuma, Acc. Chem. Res. 43, 1375 (2010).[4] Y. Andoh, N. Yoshii, A. Yamada, K. Fujimoto, H. Kojima, K. Mizutani, A. Nakagawa, A. Nomoto, S. Okazaki, J. Chem. Phys. 141, 165101 (2014).
• Quantum mechanics (QM)
• Molecular dynamics (MD)
• Linear-scaling O(N) More than 104 atoms, Long simulation time
Dynamical behavior
WFT: Wave function theory
DFT: Density functional theory
DFTB: Density-Functional Tight-Binding
MM: Molecular Mechanics
Semi-empirical model derived from density functional theory (DFT)[1,2]
Density-Functional Tight-Binding (DFTB) method
3[1] M. Elstner, G. Seifert, Phil. Trans. R. Soc. A 372, 20120483 (2014).[2] M. Gaus, Q. Cui, M. Elstner, WIREs Comput. Mol. Sci. 4, 49 (2014).
• Dμν: Density matrix
• ΔqA: Induced Mullikencharge on atom A
atom2
atomatomrep
AO0
DFTB3
1
2
1
AB
BAAB
AB
BAAB
BA
AB qqqqVHDE
DFTB1 DFTB2 DFTB3
① ② ③ ④
Evaluate using parameters determined by DFT calculations
①: Charge independent term Precomputed Hamiltonian and overlap matrices Two-center approximation
②: Short-ranged two-body repulsive term Core-core repulsion DFT double-counting contribution
③, ④: Charge dependent term Self-consistent determination of ΔqA (SCC) Monopole approximation
No integral evaluation at runtime
Proper description of chemical bonds in MD with small cost
Key ingredient for reasonable accuracy and transferability
Efficiency of DFTB: Pros and cons
4[1] M. Elstner, G. Seifert, Phil. Trans. R. Soc. A 372, 20120483 (2014).
Single-point calculation time for various molecules [s][1]
Hundreds of times faster than DFT for hundreds of atoms system
0 2000 4000 6000 8000 10000
Number of water molecules
0000
0500
1000
1500
2000
Tim
e [s
]DFTB2
O(N3.1)Cubic scaling with respect to system size is problematic for truly large systems
Combination with linear-scaling technique
Divide-and-Conquer (DC) method[1,2]
5[1] M. Kobayashi, H. Nakai, in Linear-Scaling Techniques in Computational Chemistry and Physics, (2011), pp. 97–127.[2] W. Yang, T.-S. Lee, J. Chem. Phys. 103, 5674 (1995).
…
Divide
Buffer region
Subsystem
Subsystem fragmentation without overlap
Localization region
…Conquer
SCF
Calculate• Total density matrix• Total energy• Other properties
Set common Fermi level (Conserve total number of electrons)
[1] H. Nishizawa, Y. Nishimura, M. Kobayashi, S. Irle, H. Nakai, J. Comput. Chem. 37, 1983 (2016).
④ Determination of Fermi level
• Interpolation based algorithm[1]
ε
n(ε)
εF
ne
)MO(
)(2)(
p
pp wfn
⑤ Calculate density matrix )MO(
*
F2
i
iii ccfD
A L
A SDq
)(
⑥ Calculate Mulliken charges
⑦ Calculate total Mulliken charges
SCC convergence check
③
⑦
Proton diffusion
10[1] C. J. T. de Grotthuss, Ann. Chim. 58, 54 (1806).
• Fundamental phenomenon Acid catalyst Enzymatic reaction Fuel cell design
• Proton transfer (Grotthuss shuttling) mechanism was proposed more than 200 years ago[2]
Dv: Vehicular diffusion in Eigen (H3O+) form
DG: Grotthuss diffusion via Zundel (H5O2
+) form
Forward shuttling
Backward shuttling
Dp: Overall proton
diffusion
Environmental science Porous materials design ...
Proton diffusion in bulk water
11[1] H. Nakai, A. W. Sakti, Y. Nishimura, J. Phys. Chem. B 120, 217 (2016).[2] Z. Luz, S. Meiboom, J. Am. Chem. Soc. 86, 4768 (1964).
h(t
)
thtthth
30
20
10
000 4 8 12
300 K320 K360 K400 K
Time [ps]
523H2O + 1H+, T = 300 K
T [K] This work[1] Experiment[2]
300 0.69 0.67
320 0.88 0.86
360 1.25 1.31
400 1.84 1.83
Proton transfer rate [ps−1]dt
tdhr
)(p
Forward shuttling
Backward shuttling
1
1
0
th
No shuttling
Forward
Backward
12
Proton diffusion in bulk water
[1] N. Agmon, Chem. Phys. Lett. 244, 456 (1995). [2] C. M. Maupin, B. Aradi, G. A. Voth, J. Phys. Chem. B 114, 6922 (2010). [3] P. Goyal, M. Elstner, Q. Cui, J. Phys. Chem. B 115, 6790 (2011). [4] H. Nakai, A. W. Sakti, Y. Nishimura, J. Phys. Chem. B 120, 217 (2016). [5] R. Mills, J. Phys. Chem. 77, 685 (1973). [6] S. Meiboom, J. Chem. Phys. 34, 375 (1961).[7] N. K. Roberts, H. L. Northey, J. Chem. Soc. Faraday Trans. 70, 253 (1974).
T = 300 K CPMD[2] DFTB3-diag[3] This work[4] Experiment
N(H+)/N(H2O)a 1/128 1/128 1/523
Dv [Å2/ps] 0.10b 0.38b 0.19b 0.23[5]
DG [Å2/ps] 0.23b 0.28b 0.72b 0.70[6]
Dp [Å2/ps] 0.33b 0.66b 0.91b 0.94[7]
DG/Dv 2.30b 0.74b 3.79b 3.04[6]
Dp/Dv 3.30b 1.74b 4.77b 4.09[6]
• Dp: Proton diffusion
• Dv: Vehicular diffusion
• DG: Grotthuss diffusion
• l: Proton hopping length (2.5 Å)[1]p
22
OO
Gvp66
)0()(lim r
l
t
rtrDDD
t
aNumber of species in the simulated system bDefined as Dp − Dv
Proton diffusion in bulk water
13
[kJ/mol] This work[1] Experiment[2]
ΔEv 9.69
ΔEG 9.38 10.04
ΔEp 9.47
RT
EDD
0lnln
Vehicular diffusion
Grotthuss diffusion
Proton diffusion
Grotthuss diffusion (Experiment)
2.4
1000/T [K−1]
2.6 2.8 3.0 3.2 3.4 3.6
1
ln(D
)
0
−1
−2
[1] H. Nakai, A. W. Sakti, Y. Nishimura, J. Phys. Chem. B 120, 217 (2016).[2] Z. Luz, S. Meiboom, J. Am. Chem. Soc. 86, 4768 (1964).
• ΔEv: Water diffusion barrier for protonated system
[1] P. Tans, NOAA/ESRL, (www.esrl.noaa.gov/gmd/ccgg/trends/, data accessed October 12, 2016).[2] GISTEMP Team 2016, GISS Surface Temperature Analysis (GISTEMP), (data.giss.nasa.gov/gistemp/, data accessed October 12, 2016).[3] International Energy Agency, Energy Technology Perspectives 2016, (www.iea.org/etp2016, data accessed October 12, 2016).
• CO2: Main source of greenhouse gases causing global warming
• From 6 ˚C scenario (6DS, current trends) to 2˚C scenario (2DS)
1960 1980 2000 2020
320
340
360
380
400
Year
Ato
mo
sph
eri
cC
O2
[pp
m]
−0.2
0.0
0.2
0.4
0.6
0.8
Glo
bal
tem
per
atu
re a
no
mal
y [˚
C]
CO2 at Mauna Loa
Temperature
CO2 and temperature[1,2]
Carbon capture and storage (CCS) is one of the critical components for future reduction of CO2 emissions
Technologies against CO2 emissions[3]
1990 2010 2030 2050Year
00
20
40
60
CO
2em
issi
on
[G
tCO
2]
6DS
2DS
End-use energy
Renewables
CCS
Fossil fuel
Nuclear
Power generation efficiency
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Carbon capture and storage (CCS)
[1] B. Smit, J. R. Reimer, C. M. Oldenburg, I. C. Bourg, Introduction to Carbon Capture and Sequestration, Imperial College Press, London, 2014.[2] K. Teranishi, A. Ishikawa, H. Nakai, J. Comput. Chem. Jpn. 15, A15 (2016).
• Capture CO2 from sources before releasing
• Store in geological formation through pipeline transportation
Chemical absorption is a well-known technology with industrial applicability and suitable for retrofit
Process flow of CCS[1] Main approaches in CO2 capture[2]
16
CO2 Chemical absorption
[1] K. Teranishi, A. Ishikawa, H. Nakai, J. Comput. Chem. Jpn. 15, A15 (2016).
CO2 is scrubbed with amine solution before releasing from sources
Process flow of chemical absorption[1]
Design of high performance and low cost amine solution is required
17
Reaction of amine-CO2 system[1]
[1] K. Teranishi, A. Ishikawa, H. Nakai, J. Comput. Chem. Jpn. 15, A15 (2016).
Reactant Product
Product
18
Simulation of CO2 regeneration process[1]
[1] H. Nakai, Y. Nishimura, T. Kaiho, T. Kubota, H. Sato, Chem. Phys. Lett. 647, 127 (2016).
Absorption process
Regeneration process
T = 393.15 K
5 10 15 20 25
Time [ps]
180
160
140
120
OC
O a
ngl
e [d
egre
e]
100
19
Simulation of CO2 regeneration process[1]
Collision between protonated amine (cation) and carbamate (anion)
14.8 ps8.0 ps
−+
+
−
180
160
140
120
OC
O a
ngl
e [d
egre
e]
2.5
2.0
1.5
1.0
0.5
Inte
rmo
lecu
lar
dis
tan
ce [
Å]
5 10 15 20 25Time [ps]
100
Reactive collision
Non-reactive collision17.7 ps 22.0 ps
Proton transfer
CO2
AmineAmine
Carbamate
Protonated amine
Carbamate
Protonated amine
[1] H. Nakai, Y. Nishimura, T. Kaiho, T. Kubota, H. Sato, Chem. Phys. Lett. 647, 127 (2016).
Summary and Acknowledgement
20
QM-MD Classical MDWFT DFT DFTB DC-DFTB MM
Cluster collisionElectrolyte
decompositionCarbon nanotube
growthCO2 chemical
absorptionVirus
< 100 < 1000 < 1000 ~100000 ~10000000
• Summary: Chemical reaction dynamics with DC-DFTB-MD DC: Linear-scaling computation DFTB: Small pre-factor with acceptable accuracy K: Single node to massively parallel calculation by hybrid parallelization Applications to aqueous solution systems
• Acknowledgement FLAGSHIP2020, MEXT within the priority study 5
HPCI system research project for using the K computer (Project ID: hp160215)