Pseudopotential calculations of Porphyrin Complexes

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Pseudopotential calculations of Porphyrin
Complexes
FADFT2007_at_ISSP, Japan.
Ryo Maezono
Tokyo
rmaezono_at_mac.com
School of Information Science,
Japan Advanced Institute of Science and
Technology, Ishikawa, Japan.
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JAIST
Japan Advanced Institute of Science and
Technology.
From this year
- Kiyo TERAKURA organizes new Ab-initio Group
Research Center for Integrated Science (RCIS)
- Ryo MAEZONO (DMC) _at_ Informaton Science Dept.
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Diffusion Monte Carlo
(c.f., Lectures by M. CASULA and J. Kolorenc)
- Independent from DFT framework.
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Aim
Porphyrin, Phthalocyanine etc.
- Actively studied in Nano/Bio research field.
- Interplay between TM site and Side-chains.
Establish procedures for pseudo-pot. QMC
calculations.
suitable for stable DMC accumulation.
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Background (1)
John TRAILs Pseudo potential studies.
J. Trail et.al., JCP 122, 174109 (2005).
- Non-diverging, non-local pseudo potentials.
avoiding eN-cusp.
Fock exchange.
QMC_pp
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Pathology due to Non-locality
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Interesting test case
Porphyrin, Phthalocyanine etc.
- Actively studied in Nano/Bio Science.
- Interplay between TM site and Side-chains.
Establish procedures for pseudo-pot. calculations.
suitable for stable DMC accumulation.
- Generate trial/guiding WF in pseudo-pot. calc.
- Basis set re-optimization.
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Gaussian basis set with JRT pseudo.
(John R. Trail)
commonly used in Molecular Science, Bio-molecule
bussiness as well.
preparation of proper basis set.
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Gaussian basis calculation with JRT pseudo.
Practical calculations after JRT2005
Lighter Ions.
I. Gurtubay et.al., JCP 124, 024318 (2006).
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Procedure
LANL1DZ
the same core size as JRT pseudo.
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QMC calculations
Cu-Porphyrin QMC_pp(all)
Cu
HFSCF
-206.4994
(hartree)
Variational
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Jastrow Functions
lteegt
ltengt
lteengt
- Fixed cutoff lengths Lu5.0 a.u./ L?4.0
a.u./ Lf3.0 a.u./
- N.D.Drummond, M.D.Towler and R.J.Needs Phys.
Rev. B, 70, 235119 (2004)
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Tendencies
B3LYP, DMC, MP2
Absolute values of energy
B3LYPltDMCltMP2
2 ha. (all) / 4 ha. (TM)
Energy Diff. ( binding )
? QMC not variational here.
MP2ltB3LYPltDMC
MP2ltDMCltB3LYP
Only for NiPo,
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Notes
- Atomic calculation of Zn with LANL.
Though it is QUITE simple system,
VARMIN (Variance Minimization)
wont run even with reduced parameters into one.
? Try with latest scheme such as emin/madmin??
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Summary
Replacing procedure of QMC pseudo potentials
suitable for stable DMC accumulation.
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High Performance Computing Facilities
Hitachi SR11000
Cray T3E,XT3
SGI Origin2000,Origin3000,Altix3700,Altix4700
Fujitsu PrimePower,PrimeQuest
HP GS320, ES40, ES45, GS1280
IBM SP3, p690.
Clusters Pentium3,Opteron,Macintosh(Xeon)
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Architectures