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Pseudopotential calculations of Porphyrin Complexes…

Kanazawa. FADFT2007@ISSP, Japan. . Pseudopotential calculations of Porphyrin Complexes…. Ryo Maezono. Tokyo. rmaezono@mac.com. School of Information Science,. Japan Advanced Institute of Science and Technology, Ishikawa, Japan. - Taisuke OZAKI (OPEN-MX) ; Order-N method.

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Pseudopotential calculations of Porphyrin Complexes…

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  1. Kanazawa FADFT2007@ISSP, Japan. Pseudopotential calculations of Porphyrin Complexes… Ryo Maezono Tokyo rmaezono@mac.com School of Information Science, Japan Advanced Institute of Science and Technology, Ishikawa, Japan.

  2. - Taisuke OZAKI (OPEN-MX) ; Order-N method. - Dr. Dam Hieu-Chi as lecturer @ Knowledge Science Dept. - Dr. Jae-Dong Lee as lecturer @ Materials Science Dept. 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) @ Informaton Science Dept.

  3. most practical implementation of the projection method: (Fermion Sign Problem) Fixed node DMC. projection is limited under assumed fixed node. - Can be used as accurate calibrations. rather than a tool for practical of Materials Science at THE PRESENT. Diffusion Monte Carlo (c.f., Lectures by M. CASULA and J. Kolorenc) - Independent from DFT framework.

  4. TM TM = Ni, Cu, Zn - prepare trial/guiding WF in pseudo-pot. calc. - Basis set re-optimization. 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.

  5. Lee-Needs（2002) Ovacharenko-Lester（2001) - Transition metal ions… s-electrons coexist with d-electrons.→ Difficulty! Valence electron but not HOMO John investigated long-range tail. …then wrong behavior… Asymptotic behavior of orbital functions. Trail-Needs（2005) , Dolg（2005) Background (1) JohnTRAIL’s Pseudo potential studies. J. Trail et.al., JCP 122, 174109 (2005). - Non-diverging, non-local pseudo potentials. avoiding eN-cusp. Fock exchange. ‘QMC_pp’

  6. Fock non-locality Pseudo orb. AE orbital Norm-conserving John TRAIL investigated … Asymptotic behavior of orbital functions. Valence electron but not HOMO …then wrong behavior… ‘4s’-orb. of TM ion. J. Trail et.al., JCP 122, 174109 (2005). 3d is HOMO above 4s → continuously taken over by outside. Pathology due to Non-locality

  7. TM TM = Ni, Cu, Zn 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.

  8. Conventional pseudo pot. provided with preset basis set. (such as LANL2DZ etc.) not fully optimized but well calibrated. ‘This basis set can be reliable upto XXX digit’ How to setup the basis set for JRT pseudo? → Basis set optimization by ourselves. (John R. Trail) Gaussian basis set with JRT pseudo. commonly used in Molecular Science, Bio-molecule bussiness as well. preparation of proper basis set.

  9. TM TM = Ni, Cu, Zn TM Ions. <Aim> - Porphyrin calculations. - See how’s going on TM pseudo by John’s remedy. The system is too large to be dealt with ‘Billy’. → Basis set optimization manually. Gaussian basis calculation with JRT pseudo. Practical calculations after JRT2005 Lighter Ions. I. Gurtubay et.al., JCP 124, 024318 (2006).

  10. Structure optimization in B3LYP <Porphyrin> Replace TM Pseudo (from LANL to JRT) Re-optimize TM basis set TM QMC_pp(TM) TM = Ni, Cu, Zn H,C,N are treated as AE (6-31G**). Replace AE by JRT-Pseudo. <Porphin> QMC_pp(all) Re-optimize H,C,N basis set @ porphin. Procedure LANL1DZ the same core size as JRT pseudo.

  11. MP2 -210.2612 VMC -210.693(1) DMC B3LYP -211.5698(9) -212.7404 Non-variational QMC calculations Cu-Porphyrin [QMC_pp(all)] Cu HFSCF -206.4994 (hartree) Variational

  12. - Optimization ; Unreweighted SC Variance Minimization. - N.D.Drummond and R.J.Needs; Phys. Rev. B, 72, 085124 (2005) Jastrow Functions… <ee> <en> <een> - Fixed cutoff lengths ; Lu=5.0 a.u./ Lχ=4.0 a.u./ Lf=3.0 a.u./ - N.D.Drummond, M.D.Towler and R.J.Needs; Phys. Rev. B, 70, 235119 (2004)

  13. [TMPo/Atom/Po] [QMCpp(TM)/QMCpp(all)] Tendencies B3LYP, DMC, MP2 Absolute values of energy B3LYP＜DMC＜MP2 2 ha. (all) / 4 ha. (TM) Energy Diff. ( ‘binding’ ) ※QMC not variational here. MP2＜B3LYP＜DMC Only for NiPo, MP2＜DMC＜B3LYP

  14. Notes - Atomic calculation of Zn with LANL. Though it is QUITE simple system, VARMIN (Variance Minimization) won’t run even with reduced parameters into one. →Try with latest scheme such as emin/madmin??

  15. LANL pseudo/basis set … easy to get and calculate in SCF. as it is replace with JRT pseudo re-optimization of basis set No stable DMC Stable DMC accumulation. δE~0.001 hartree Summary Replacing procedure of QMC pseudo potentials suitable for stable DMC accumulation.

  16. 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)

  17. - SGI Altix @JAIST (360 procs) Itanium2, 24GB/4cpu - Cray XT3 @JAIST (128 procs) Opteron150, 32GB/4cpu - Hitachi SR11000 @Hokkaido Univ. (640 procs) IBM Power5+, 128GB/16cpu - Macintosh @JAIST (96 procs, my own!) Xeon, 16GB/4cpu Architectures

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