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CPMD: design and characterization of innovative materials Mauro Boero Institut de Physique et Chimie des Matériaux de Strasbourg, UMR 7504 CNRS-UDS, 23.

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Presentation on theme: "CPMD: design and characterization of innovative materials Mauro Boero Institut de Physique et Chimie des Matériaux de Strasbourg, UMR 7504 CNRS-UDS, 23."— Presentation transcript:

1 CPMD: design and characterization of innovative materials Mauro Boero Institut de Physique et Chimie des Matériaux de Strasbourg, UMR 7504 CNRS-UDS, 23 rue du Loess, BP 43, F Strasbourg, France and CREST, Japan Science and Technology Agency, Kawaguchi, Saitama , Japan, and JAIST, Hokuriku, Ishikawa, Japan

2 Outline CPMD: a quick overview of the basics of the code and advanced tools for simulating reactive processes reaction Synthetic organic reactions -  -Caprolactam (Nylon-6) production without using acid catalysts: - Catalytic properties of water above the critical point - Tuning the efficiency and selectivity of the reaction

3 What do we want to do ? And which are main the ingredients ? electron- electron ion-ion electron - ion electron- ion i(x)i(x) RIRI

4 Car-Parrinello Molecular Dynamics Solve the Euler-Lagrange equations of motion

5 BO surface CP trajectory BO trajectory The difference between the CP trajectories R I CP (t) and the Born-Oppenheimer (BO) ones R I BO (t) is bound by | R I CP (t) - R I BO (t)| < C  1/2 (C > 0) if F.A. Bornemann and C. Schütte, Numerische Mathematik vol.78, N. 3, p (1998)

6 R space  G space Plane wave basis set:  i (x) =  G c i (G) e iGx For each electron i =1,…,N, G = 1,…,M are the reciprocal space vectors. The Hilbert space spanned by PWs is truncated to a cut-off G cut 2 /2 < E cut E 2 cut > E 1 cut E 1 cut

7 G space R space ci(G)ci(G) i(x)i(x)  G c i (G) G 2 {E k } V NL (G) {E NL }  (G) N*FFT FFT  (x) (x) V loc (G) + V H (G) {E loc +E H } = V LH (G) V xc (x) {E xc } + V LH (x) = V LOC (x); V LOC (x)  i (x) FFT N*FFT V LOC (G)c i (x) + V NL (G) +  G c i (G) G 2

8 Practical implementation G=1,…,M (loop on reciprocal vectors) are distributed (via MPI/OMP) in a parallel processing in bunches of M/(nproc) i=1,…,N (loop on electrons) is distributed (via MPI/OMP) I=1,…,K (loop on atoms) generally does not require parallelization (vectorized and distributed via OMP) The scaling of the algorithm is O(NM)for the kinetic term, O(NM logM) for the local potential and O(N 2 M) for the non-local term and orthogonalization procedure (all other quantum chemical methods scale as O(MN 3 ) M=basis set) - -

9 ES system configuration Parallel vector supercomputer system with 640 processor nodes (PNs) connected by 640x640 single-stage crossbar switches. Each PN is a system with a shared memory, consisting of - 8 vector-type arithmetic processors (APs): total=5120 AP - a 16-GB main memory system (MS) - a remote access control unit (RCU) - an I/O processor. MPI

10 ES system : single processor node (PN) The overall MS is divided into 2048 banks The sequence of bank numbers corresponds to increasing addresses of locations in memory. OMP

11 From reactants A to products B: we have to climb the mountain minimizing the time A general chemical reaction starts from reactants A and goes into products B The system spends most of the time either in A and in B …but in between, for a short time, a barrier is overcome and atomic and electronic modifications occur Time scale: 

12 Escaping the local minima of the FES: In one dimension, the system freely moves in a potential well (driven by MD). Adding a penalty potential in the region that has been already explored forces the system to move out of that region, but always choosing the minimum energy path, i.e. the most natural path that brings it out of the well. Providing a properly shaped penalty potential, the dynamics is guaranteed to be smooth and therefore the systems explores the whole well, until it finds the lowest barrier to escape. V(s)V(s) s

13 t0t0 t1t1 t2t2 脱出 F(s)F(s) F(s)+V(s, t) ss s(t0)s(t0) t3t3 ∙∙∙∙∙ Set up collective variables {s  } and parameters M , k ,  s, A Perform few MD steps under harmonic restraint Add a new Gaussian Update mean forces on {s  } Update {s  } The component of the force coming from the gaussians subtracts from the “true” force the probability to visit again the same place

14 How to plug all this in CPMD ? We simply write a (further) extended Lagrangean including the new degrees of freedom History-dependent potential Fictitious kinetic energy Restrain potential: coupling fast and slow variables √(k α /M α ) « ω I

15 Collective (dynamical) variables Velocity Verlet algorithm to solve the equations of motion two contributions to the force

16 Beckmann rearrangement: 1.Commercially important for production of synthetic fibers 2.Known to be catalyzed only by strong acids in conventional non-aqueous systems 3.Formation of byproducts (ammonium sulfate, (NH 4 ) 2 SO 4 ) of low commercial value in acid catalyst: byproducts = 1.7 × products (in weight). See (e.g.) 4.Environmentally harmful: acid wastes are produced Points 2, 3 and 4 and related problems can be eliminated in scH 2 O: no acid required & no byproducts. See Y. Ikushima et al. J. Am. Chem. Soc. 122, 1908 (2000); Work done on collaboration with: Michele Parrinello, Kiyoyuki Terakura, Tamio Ikeshoji and Chee Chin Liew

17 World wide production of  -caprolactam EuropeUSAJapan BASF 434Honeywell 341UBE 180 Bayer 155BASF-USA 270Toray 180 DOMO 100DSM 200Sumitomo 160 UCHE 85Evergreen 45Mitsubishi 120 unit = 1000 ton/year

18 Hydrogen-bond network in water T = 300 K  = 1.00 g/cm 3 T=653 K  =0.73 g/cm 3 Continuous hydrogen-bond NWDisrupted hydrogen-bond NW Normal water Supercritical water

19 Beckmann rearrangement reaction in strong acid and supercritical H 2 O hydrolysis in H 2 O and superheated H 2 O proton attack to O proton attack to N

20 Which are the important ingredients that make water special at supercritical conditions ? Proton attack is the trigger (experimental outcome !) fast proton diffusion difference in hydration between O and N High efficiency : High selectivity :

21 ~ 0.9 ps in scH 2 O ~ 5.2 ps in n-H 2 O Contrary to normal liquid water, scH 2 O accelerates selectively the formation of the first intermediate Proton attack to N: Cycrohexanon (byproduct) formation

22 Efficient reaction in scH 2 Odue to fast proton diffusion and acid properties of the (broken) Eigen-Zundel complexes Acid catalyst ?

23 Cyclohexanone-oxyme in scH 2 O : The energy barrier seems rather high and the reaction pathway not unique The reaction is generally acid catalyzed, hence protons are expected to be essential in triggering the process At supercritical conditions, however, the K w of water increase, hence H + and OH - can be around in the solvent in non-negligible concentration And small amounts of weak acids greatly enhance reaction rates

24 Proton diffusion in ordinary liquid and supercritical water Is the proton diffusion slowed down in scH 2 O ? Not really… Hydrogen bond network is disrupted in SCW.

25 Proton diffusion : normal water and supercritical water Proton (structural defect) diffusion coefficient estimation in the 3 systems: System Diffusion constant D (cm 2 /s) Hydrogen bond network n-H 2 O (normal water) 15.0 x continuous Superheated H 2 O 62.0 x continuous (fast switch) scH 2 O (supercritical water) 55.0 x disrupted In scH 2 Othe network is disrupted and the motion occurs in sub-networks that join and break apart rapidly due to density fluctuations; two diffusion regimes are cooperating: hydrodynamics (vehicular) and Grotthus

26 Selective reaction in scH 2 O due to different solvation of O and N Reaction selectivity ?

27 H+H+ T = 673 K wet dry Cyclohexanone-oxyme in scH 2 O (+ H + ): the selectivity

28 Cyclohexanone-oxyme in scH 2 O (+ H + ) R—C—R ’ N—OH H+H+ R—C—R’ N+N+ + H 2 O R—N = C + —R’ A very small activation barrier (about 1 kcal/mol) is required for the N insertion process.

29 …and now the second step: C-O bond formation  E = 5.9 kcal/mol  F = 5.1 kcal/mol Approach of an H 2 O molecule,  = |O wat -C|

30 + H 2 O R—C—R’ N+N+ H+H+ R—N = C—R’ HO R—N = C—R’ HO O H H R—C—R’ N—OH oxime R—N—C—R’ OH amide H2OH2O R—N = C + —R’ OH - H The last step:eventually the  -caprolactam

31 The last step:eventually the  -caprolactam Proton exchange in scH 2 O (metadynamics)

32 Free energy surface: a less rugged landscape s 1 = 0.5 s 1 = 1.0

33 Conclusions and perspectives The H + diffusion in scH 2 O occurs in sub-networks that join and break rapidly due to density fluctuations: two diffusion regimes are present. Destabilization of Eigen (Zundel) complex makes scH2O an acid-like environment able to trigger chemical reaction The selectivity of the cyclohexanone-oxyme to  -caprolactam reaction could be understood The role of the H-bond in differentiating the solvation features of the solute has been evidenced A new green chemistry perspective has been explored. Related Publications: M.B. et al., Phys. Rev. Lett. 85, 3245 (2000); J. Chem. Phys. 115, 2219 (2001); Phys. Rev. Lett. 90, (2003) ; J. Am. Chem. Soc. 126, 6280 (2004); ChemPhysChem 6, 1775 (2005)

34 Acknowledgements Michele Parrinello, ETHZ-USI and Pisa University Roberto Car, Princeton University Kiyoyuki Terakura, JAIST, AIST and Hokkaido University Michiel Sprik, Cambridge University Pier Luigi Silvestrelli, Padova University Alessandro Laio, SISSA, Trieste Jürg Hutter, Zurich University Marcella Iannuzzi, Zurich Univeristy Carlo Massobrio, IPCMS

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