Thanh Ngoc Pham,1* Yuji Hamamoto,1,2 Kouji Inagaki,1,2 Ikutaro Hamada,1,2 andYoshitada Morikawa1,2,3
1Department of Precision Engineering, Osaka University, 2-1 Yamada-Oka, Suita, Osaka 565-0871, Japan,
2Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto

615-8520, Japan.
3Research Center for Ultra-Precision Science and Technology, Graduate School of Engineering, Osaka
University, 2-1 Yamada-oka, Suita 565-0871, Osaka, Japan*Email: thanh@cp.prec.eng.osaka-u.ac.jp

I. Introduction

III. Results and discussion• The complex formation of nitric oxide

A. NO and H2O clusters on Cu(111)••(NO) with some common gases inthree-way catalyst environment (e.g.
NH3, H2O. etc.) is important for theselectivity of the NO reduction reaction.
Recently, the formation of NO-H2O
complex on Cu(111) is observed
experimentally [1].
It found that NO-H2O interaction isstronger than NO-NO and H2O-H2O
interactions, leading to the formation ofa mixed NO-H2O complex on Cu(111)[1]
To shed light on the experimental
observation of NO-H2O/Cu(111), we
studied the adsorption of small mNOnH2O complexes (n = 1 – 4, m = 1 – 4)
on Cu(111) [2]NO-NO

H-bond (HO-H⋅⋅⋅OH2 )NO and H2O tend to form
small clusters upon
individual adsorption
Eb = 0-0.12

0.00

-0.28

-1.37 eVB. NO-H2O co-adsorption on Cu(111)
Binding strength per bond /meV•

HO-H⋅⋅⋅ON)••HO-H⋅⋅⋅ON)(H 2OH2ON

4
14−n3−m(NO)3 + (H2O)6 → nNO-mH2O +(NO)3 +(H2O)63236Eb/eV ∆q(NO)/e ∆q(H2O)/eNO monomer

NO monomer

0-0.60NO in NO-H2O

H2O monomer

0NO-H2O-0.222

0.02

ff

0.02

Δq = Z − q,

Where Z and q are total valance and Baderelectrons

H-bond (HO-H⋅⋅⋅ON)
Mainly electrostatic attraction (major)[3] Y. Morikawa, Phys. Rev. B 51, 802, (1995)

fi-0.77∆q : e ective Bader charge-0.60e+

•O
3N

ΔE

tot
tot
tottotEb(nNO-mH2O) = EnNO−nE−
mE+(n+m−1)E-mH2O/Cu
NO/Cu
H2O/CuCu,

stronger than NO-NO and H2O-H2Ointeraction.
NO-H2O interaction mainly arises fromdirect hydrogen bondings between H2Oand negatively charged NO by backdonation process.

2OH(2OH-3C. Intermolecular interaction

tottottot
totEads(nNO-mH2O) = EnNO-mH2O/Cu − [ECu + nENO + mEH2O]

IV. Conclusions• We con rm the NO-H2O interaction is)6

HO-H⋅⋅⋅ONNO-NOPDOS•(NO) 2stable than (NO)3 and (H2O)6.
• H-bond saturation leads to amore stable mixed complex
structure even though theirbinding strength is weaker

II. Computational details• DFT with STATE (Simulation Tool forAtom TEchnology) package. [3]Plane-wave basis set with cut-oenergies of 36 and 400 Ry for wave
functions and augmented charge
density.
K-points: 5 x 5 x 1
Eight-layer slab model for Cu(111) witha vacuum thickness of 16 ÅO) 3• NO-H2O complexes are more

[1] H. Koshida et al, J. Phys. Chem C 122, 8894 (2018)[2] T. N. Pham et al. Phys Rev Mat. Under review

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A density functional theory study on NO-H2O coadsorption on Cu(111)-ΔρNO-H2O = ρNO-H2O/Cu − ρNO/Cu − ρH2O/Cu + ρCuH-bond (electrostatic attraction between H2O andnegatively charged NO) mainly stabilizes the coadsorption and enhances the back donation to 2π* orbitals--0.77eerich

H2O

e-+

Attraction by
induced e- transfer(minor)

e- by backdonation

NO-H2ONO

Schematic for NO-H2O interaction

JHPCN
ID: EX22202
Title: First-principles multiscale simulation of sintering process of perovskite-supported metal nanoclusters