50k granted to Comp_POP_Catalysts for the rest of the year. JB On Mon, Feb 29, 2016 at 9:09 AM, Bair, Raymond A. <[email protected]> wrote:

Looks OK to me. Suggest we approve.

Ray

On 2/26/16, 1:59 AM, "[email protected] on behalf of [email protected]" <[email protected] on behalf of [email protected]> wrote:

...

Hello,

A change in allocation has been requested:

Requester: kongf (Fanjie Kong) Project: Comp_POP_Catalysts Title: Computational studies of copper metalated catechol-containing porous organic polymers catalysts Description: The planned computations will explore the structural, energetic, electronic, and catalytic functionality of copper incorporated catechol-containing POPs. Our studies will include the investigation of the structure and electronic structure, e.g. the charge state, along with the chemical functionality of active sites, composed of single or two copper atoms, incorporated onto catechol-containing POPs. The effects of ligands on these physical and chemical properties will also be explored. One of the candidates for catalytic transformations to be tested is the selective oxidation of benzyl alcohol to benzaldehyde. The activity and selectivity difference in the oxidation reaction of benzyl alcohol between single and two copper atoms containing catechol-containing POPs will be compared and explained, in correlation with the structural, charge and electronic structure analysis. The choices for the catechol-containing POPs and catalytic transformations are ma de based on the planned experimental investigations, some of which are currently undergoing.

Within the planned studies, the issues that will be addressed are:

1) Activity and selectivity of single and two copper atoms containing catechol-containing POPs in the oxidation of benzyl alcohol. In this respect, computations have been partly performed for optimizing single and two copper atoms incorporated into catechol-containing POPs. These studies have been extended to single and two copper atoms containing catechol-containing POPs decorated with H2O, CH3OH and CH3CN as ligands.

2) Use of oxygen molecule to probe the oxygen activation of copper sites of single and two atoms supported on catechol-containing POPs. Here we plan to explore the most preferred adsorption form (molecular adsorption or dissociative adsorption), the most preferred adsorption conformation and the reaction pathway for adsorption. For this purpose some computations have been performed, where the potential energy surfaces are studied as a function of the distance between the mass center of oxygen molecule and copper for single copper catechol-containing POPs (the mass center of two copper atoms catechol-containing POPs).

3) Use of benzyl alcohol, in particular the concentration as a selectivity knob for selective oxidation of benzyl alcohol. We will particularly address the energetics of the benzyl alcohol adsorption as a function of benzyl alcohol concentration.

4) Our calculations on DFT-based assignment of infrared (IR) spectra of catecholate POP have shown an excellent agreement with the measured spectra. Hence, we aim to use the computed and the measured IR spectra as a tool for identification of the actual conformations of single and two copper atoms containing catechol-containing POPs.

The computational studies of the structural, energetic, and electronic structure aspects will be performed using density functional theory. The packages that will be utilized include VASP, NWChem, CP2k and Crystal. Naturally, we will benefit from the efficient scaling of the codes and take advantage of it in order to explore systems with still increasing number of atoms. Thus in our project: 1) The study of the structural and electronic properties for single and two copper atoms containing catechol-containing POPs, and 2) the relation of these properties with the catalytic functionality, are research subjects which suit well with the high-performance infrastructure of the LCRC computational resources. Current: undetermined amount Justification: The scaling efficiency on Fusion was tested using the code NWCHEM in geometry optimization of single copper catechol porous organic polymer, which contain a total of 95 atoms: 40 atoms of H (2 basis function per H), 49 atoms of C (14 basis function per C), 4 atoms of O (14 basis function per O) and 2 atoms of Cu (35 basis function per Cu); a total of 962 basis functions. Substantial speed-up is achieved with the increase in the number of cores:

Cores Average SCF cycle (s) 96 1500 128 1000

Requested: 50000

A specific reason has been given: More calculations are needed to identify the structures of two copper containing catecholPOPs with ligands.The allocation time for the second quarter was used up. Additional computation time is needed to finish the calculations.

This needs to be approved and the final allocation amount decided upon.

Thank You, The LCRC Accounts System _______________________________________________ allocations-admins mailing list [email protected] https://lists.lcrc.anl.gov/mailman/listinfo/allocations-admins

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