Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields
-
Upload
molmodbasics -
Category
Documents
-
view
1.278 -
download
0
description
Transcript of Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields
![Page 1: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/1.jpg)
Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields
The Effec(ve Fragment Molecular Orbital Method
Jan H. Jensen and Casper Steinmann University of Copenhagen
Dmitri Fedorov AIST, Japan
JPC A 2010, 114, 8705 PLoS ONE 2012, 7:e41117 PLoS ONE 2012, 7:e44480 arxiv.org/abs/1212.6172
1
![Page 2: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/2.jpg)
The Fragment Molecular Orbital (FMO2) method (and most other fragmentaEon methods)
2
![Page 3: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/3.jpg)
The Fragment Molecular Orbital (FMO2) method (and most other fragmentaEon methods)
Many-‐body PolarizaEon:
Monomer SCF in the Coulomb field of all other monomers
Iterated to self-‐consistency
3
![Page 4: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/4.jpg)
The Fragment Molecular Orbital (FMO2) method (and most other fragmentaEon methods)
Non-‐Coulomb effects:
Dimer SCF in the Coulomb field of all other monomers
Iterated to self-‐consistency
4
![Page 5: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/5.jpg)
The Fragment Molecular Orbital (FMO2) method (and most other fragmentaEon methods)
Coulomb effects:
Coulomb energy in the Coulomb field of all other monomers
5
![Page 6: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/6.jpg)
The EffecEve Fragment Molecular Orbital (EFMO) method (Using ideas from the EffecSve Fragment PotenSal (EFP) method)
Monomer SCF in the gas phase
Extract mulSpoles and dipole polarizability
6
![Page 7: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/7.jpg)
The EffecEve Fragment Molecular Orbital (EFMO) method (Using ideas from the EffecSve Fragment PotenSal (EFP) method)
Many-‐body polarizaEon
Computed classically using induced dipoles for enSre system
7
![Page 8: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/8.jpg)
The EffecEve Fragment Molecular Orbital (EFMO) method (Using ideas from the EffecSve Fragment PotenSal (EFP) method)
Coulomb and Non-‐Coulomb effects
dimer SCF in the gas phase
8
![Page 9: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/9.jpg)
The EffecEve Fragment Molecular Orbital (EFMO) method (Using ideas from the EffecSve Fragment PotenSal (EFP) method)
Coulomb effects
Computed using staSc mulSpoles
9
![Page 10: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/10.jpg)
MP2 (DFT doesn’t scale well)
+ 0
10
![Page 11: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/11.jpg)
Covalent FragmentaEon (ElectrostaSc screening crucial)
11 PLoS ONE 2012, 7:e44480
![Page 12: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/12.jpg)
Implemented in GAMESS With gradients
Trp cage (20 residues) 2 residues/fragment
EFMO FMO2 Error in energy -‐4.3 6.4 kcal/mol
MP2/6-‐31G(d) gradient 314 409 minutes 20 cores (most Sme spent in MP2 dimers)
12
PLoS ONE 2012, 7:e44480
![Page 13: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/13.jpg)
QM/”MM”
AcSve
Frozen
EEFMO = EA + EA /F + EF
EEFMO = EA0 + EAJ
0 − EA0 − EJ
0 − EIJPOL( )
J∈F
RI ,J ≤Rcut
∑ + EAJES
J∈F
RI ,J >Rcut
∑ + EtotPOL
h^p://arxiv.org/abs/1212.6172
![Page 14: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/14.jpg)
14
Proof-‐of-‐concept arxiv.org/abs/1212.6172
ONIOM: MP2/cc-‐pVDZ:EFMO-‐RHF/6-‐31G(d)
16 Å
ΔH ≠ = 18 vs 13 (exp)
4 days/path 80 CPUs
![Page 15: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/15.jpg)
To Do MP2:RHF-‐D opSmizaSon
EFMO/PCM Flexible EFP/Polarizable “Force Field”
(EFMO sSll quite slow for large acSve regions)
EEFMO = EI0
I
N
∑ + EIJES + EIJ
XR /CT + EIJDisp( )
IJ
N
∑ + EtotPOL
EFMO GUI: FRAGIT.org (Mikael Ibsen)
15
![Page 16: Blurring the boundary between linear scaling QM, QM/MM and polarizable force fields](https://reader033.fdocuments.us/reader033/viewer/2022051610/54872748b47959ce0c8b5408/html5/thumbnails/16.jpg)
Funding: EU (IRENE collab program)
Thank You!
QuesEons Now?
QuesEons Later?
Leave a comment on
hZp://proteinsandwavefuncEons.blogspot.com/2013/01/new-‐presentaEon-‐blurring-‐boundary.html
16