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Pseudopotential calculations of Porphyrin Complexes…

Kanazawa. TTI2007@Tuscany, Italy. Pseudopotential calculations of Porphyrin Complexes…. Ryo Maezono. Tokyo. rmaezono@mac.com. School of Information Science,. Japan Advanced Institute of Science and Technology, Kanazawa, Japan. TM. TM = Ni, Cu, Zn.

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Pseudopotential calculations of Porphyrin Complexes…

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  1. Kanazawa TTI2007@Tuscany, Italy. Pseudopotential calculations of Porphyrin Complexes… Ryo Maezono Tokyo rmaezono@mac.com School of Information Science, Japan Advanced Institute of Science and Technology, Kanazawa, Japan.

  2. 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.

  3. People involved… - Mr. Jun Koseki Gaussian SCF calc./ structure optimization. - Prof. Masanori Tachikawa - Ryo MAEZONO. Basis set optimization / QMC calc. - Prof. Richard Needs group QMC code implementation. (CASINO ; QMC code.)

  4. 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) John’s Pseudo potential studies. - Non-diverging, non-local pseudo potentials. avoiding eN-cusp. Fock exchange. ‘QMC_pp’

  5. Fock non-locality Pseudo orb. AE orbital Norm-conserving John 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

  6. 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.

  7. 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. MDT has rich experiences on this. ‘Billy’ utility (his first script with mysterious name) Gaussian basis set with JRT pseudo. commonly used in Molecular Science, Bio-molecule bussiness as well. preparation of proper basis set.

  8. 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). She used ‘Billy’ utility for basis set optimization.

  9. 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. TM Procedure LANL1DZ the same core size as JRT pseudo.

  10. Uncontracted -1020.970 3*s(1), 2*p(1), and 5*d(1) Optimized -1021.036 (hartree) • Gaussian exponents are optimized in HFSCF. - From inner most to outer, d(inner) most effective. Basis Set optimization (TM) <Porphyrin> <Ni@NiPo> Ni Initial -1020.612 (hartree) (LANL1DZ) s(3), p(2), and d(5)

  11. Basis Set optimization (C, N, H) <Lighter atoms @ Porphin> Initial -154.242 (6-31G**) (※LANL1D2) Optimized -155.612 (hartree)

  12. of NiPo -0.16894 Initial JRT pseudo with LANL1DZ 0.22476 Optimized (hartree) (c.f. 0.29691by AE) TM TM Energy difference “Not depending on Core size ” … similar as ‘binding energy’

  13. 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

  14. - 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)

  15. NotYet NotYet Energy differences Cu-Porphyrin Cu Cu DMC OPTVMC HFSCF B3LYP MP2 AE NotYet 0.35248 0.39517 0.42870 LANLsmall NotYet 0.20359 0.28371 0.18091 LANLlarge Unstable 0.063(2) 0.19622 0.21771 0.17061 QMC_pp(TM) 0.249(2) 0.178(2) 0.29338 0.26160 0.33397 QMC_pp(all) 0.170(1) 0.29309 0.230(1) 0.33404 0.25533 (hartree) reduced time step, Casula’s scheme, frequent updating.

  16. [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

  17. Notes - Atomic calculation of Zn with LANL. Though it is QUITE simple system, VARMIN (CASINO ｖ1.8.2) won’t run even with reduced parameters into one. →Try with latest CASINO with emin/madmin??

  18. 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.

  19. 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)

  20. - 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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