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

2. JAIST Research Center for Integrated Science (RCIS) Japan Advanced Institute of Science and Technology. - Kiyo TERAKURA organizes new Ab-initio Group… - Ryo MAEZONO (DMC) @ Informaton Science Dept. From this year… - 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.

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

4. Aim TM = Ni, Cu, Zn TM Establish procedures for pseudo-pot. QMC calculations. Porphyrin, Phthalocyanine etc. - Actively studied in Nano/Bio research field. - Interplay between TM site and Side-chains. - prepare trial/guiding WF in pseudo-pot. calc. - Basis set re-optimization. suitable for stable DMC accumulation.

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

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

7. TM = Ni, Cu, Zn TM Interesting test case Establish procedures for pseudo-pot. calculations. Porphyrin, Phthalocyanine etc. - Actively studied in Nano/Bio Science. - Interplay between TM site and Side-chains. - Generate trial/guiding WF in pseudo-pot. calc. - Basis set re-optimization. suitable for stable DMC accumulation.

8. Gaussian basis set with JRT pseudo. commonly used in Molecular Science, Bio-molecule bussiness as well. 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’ → Basis set optimization by ourselves. How to setup the basis set for JRT pseudo? preparation of proper basis set. (John R. Trail)

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

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

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

12. Jastrow Functions… - Fixed cutoff lengths ; L u =5.0 a.u./ L χ =4.0 a.u./ L f =3.0 a.u./ - N.D.Drummond, M.D.Towler and R.J.Needs; Phys. Rev. B, 70, 235119 (2004) - Optimization ; Unreweighted SC Variance Minimization. - N.D.Drummond and R.J.Needs; Phys. Rev. B, 72, 085124 (2005)

13. Tendencies Absolute values of energy 2 ha. (all) / 4 ha. (TM) B3LYP ＜ DMC ＜ MP2 Energy Diff. ( ‘binding’ ) MP2 ＜ B3LYP ＜ DMC [TMPo/Atom/Po][QMCpp(TM)/QMCpp(all)] MP2 ＜ DMC ＜ B3LYPOnly for NiPo, ※ QMC not variational here. B3LYP, DMC, MP2

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

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

16. High Performance Computing Facilities… * Cray; T3E,XT3 * SGI; Origin2000,Origin3000,Altix3700,Altix4700 * Clusters; Pentium3,Opteron,Macintosh(Xeon) * IBM; SP3, p690. * HP; GS320, ES40, ES45, GS1280 * Hitachi; SR11000 * Fujitsu; PrimePower,PrimeQuest

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