Formation of unique trimer of nitric oxide on Cu(111)

Shiotari, Akitoshi; Hatta, S.; Okuyama, Hiroshi; Aruga, Tetsuya

doi:10.1063/1.4896558

Cited by 19 publications

(40 citation statements)

References 56 publications

(66 reference statements)

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“…Our finding is consistent with previous theoretical studies 5,26,59−62 and STM observations by Shiotari and co-workers. 30 We confirmed that the conclusion is not changed when the slab thickness is increased (Table S1).…”

Section: Resultssupporting

confidence: 68%

“…The adsorption site of NO on Cu(111) was originally assigned to a 2-fold bridge site 13 and later it was assigned to a 3-fold hollow site. 17 Koshida et al revisited this system by EELS at 100 K and verified the formation of the NO trimer on Cu(111) that is observed by STM, 30 and the mode at 190 meV is reassigned to the N−O stretching modes of NO trimer rather than the NO monomer at the fcc-hollow site. 32 As will be discussed below, we found that the stretching modes are blue-shifted when NO absorbed in the trimer configuration, and those modes for the NO trimer agree well with the aforementioned experimental data.…”

Section: Resultsmentioning

confidence: 88%

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Insight into Trimeric Formation of Nitric Oxide on Cu(111): A Density Functional Theory Study

et al. 2020

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We have studied the adsorption of small nitric oxide (NO) clusters [(NO) n (n = 1−3)] on Cu(111), by means of the van der Waals density functional. We have found that a single NO molecule preferably adsorbs in an upright N-down configuration at the fcc-hollow site, whereas all constituent NO molecules of the NO dimer and trimer adsorb at the fcc-hollow sites, in inclined Ndown geometries. Among three NO clusters, the NO trimer is the most stable regardless of lateral periodicities, in good agreement with the scanning tunneling microscopy experiment. van der Waals interaction dominates the stabilization of the NO dimer, while the hybridization among 2π* orbitals of NO plays an important role in addition to the van der Waals interaction in the formation of the NO trimer. The relatively weak interaction between the NO and Cu substrate is crucial for the stabilization of the NO trimer. Our vibrational analysis has revealed that the N−O stretching mode is blue-shifted from monomer to trimer, and the latter agrees well with the electron energy loss spectroscopy data.

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Section: Resultssupporting

confidence: 68%

Section: Resultsmentioning

confidence: 88%

Insight into Trimeric Formation of Nitric Oxide on Cu(111): A Density Functional Theory Study

et al. 2020

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“…Nitric oxide (NO) molecules on Cu surfaces have been prominent systems to monitor the local electronic states with STM images and STS measurements [35][36][37]. For an isolated NO molecule adsorbed onto Cu(110) at ∼15 K, the resonance state of its valence orbital (2π * ) remains at E F , and therefore, the orbital is visible in the STM image at low bias voltage [36].…”

Section: Introductionmentioning

confidence: 99%

Role of valence states of adsorbates in inelastic electron tunneling spectroscopy: A study of nitric oxide on Cu(110) and Cu(001)

et al. 2016

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We studied nitric oxide (NO) molecules on Cu(110) and Cu(001) surfaces with low-temperature scanning tunneling microscopy (STM) and density functional theory (DFT). NO monomers on the surfaces are characterized by STM images reflecting 2π * resonance states located at the Fermi level. NO is bonded vertically to the twofold short-bridge site on Cu(110) and to the fourfold hollow site on Cu(001). When NO molecules form dimers on the surfaces, the valence orbitals are modified due to the covalent bonding. We measured inelastic electron tunneling spectroscopy (IETS) for both NO monomers and dimers on the two surfaces, and detected characteristic structures assigned to frustrated rotation and translation modes by density functional theory simulations. Considering symmetries of valence orbitals and vibrational modes, we explain the intensity of the observed IETS signals in a qualitative manner.

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“…22,35 (NO) 2 dimers have also been imaged on Cu(110) using scanning tunneling microscopy (STM), 33 and more recently, evidence for the formation (NO) 3 trimers on Cu(111) at 6 K has been collected with STM. 36 Nitric oxide also forms dimers on Pd(111) under certain conditions, as revealed by in situ infrared reflection absorption spectroscopy (IRAS). 37 Calculations performed on several different catalyst systems also support the intermediacy of an (NO) 2 dimer during nitric oxide reduction.…”

Section: Introductionmentioning

confidence: 99%

Understanding the Role of Hyponitrite in Nitric Oxide Reduction

Wright

Hayton

2015

Inorg. Chem.

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Herein, we review the preparation and coordination chemistry of the cis and trans isomers of hyponitrite, [N 2 O 2 ] 2-. Hyponitrite is known to bind to metals via a variety of bonding modes. In fact, at least eight different bonding modes have been observed, which is remarkable for such a simple ligand. More importantly, it is apparent that the cis isomer of hyponitrite is more reactive than the trans isomer, as the barrier of N 2 O elimination from cis-hyponitrite is lower than that of trans-hyponitrite. This observation may have important mechanistic implications for both heterogeneous NO x reduction catalysts and NO Reductase. However, our understanding of the hyponitrite ligand has been limited by the lack of a general route to this fragment, and most instances of its formation have been serendipitous.3

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Formation of unique trimer of nitric oxide on Cu(111)

Cited by 19 publications

References 56 publications

Insight into Trimeric Formation of Nitric Oxide on Cu(111): A Density Functional Theory Study

Insight into Trimeric Formation of Nitric Oxide on Cu(111): A Density Functional Theory Study

Role of valence states of adsorbates in inelastic electron tunneling spectroscopy: A study of nitric oxide on Cu(110) and Cu(001)

Understanding the Role of Hyponitrite in Nitric Oxide Reduction

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