Imaging Covalent Bonding between Two NO Molecules on Cu(110)

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

doi:10.1103/physrevlett.106.156104

Cited by 33 publications

(50 citation statements)

References 20 publications

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“…18,[24][25][26][27][28][29][30][31] However, more recent experimental work suggests an 4 alternate mechanism could also be operative. In this pathway, NO reduction proceeds via a "hyponitrite-like" (NO) 2 dimer (Scheme 1b), 20,22,[32][33][34] and, in fact, this intermediate has been detected directly with IR spectroscopy on Ag(111) at low temperatures (70 K). 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.…”

Section: Introductionmentioning

confidence: 99%

“…In this pathway, NO reduction proceeds via a "hyponitrite-like" (NO) 2 dimer (Scheme 1b), 20,22,[32][33][34] and, in fact, this intermediate has been detected directly with IR spectroscopy on Ag(111) at low temperatures (70 K). 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).…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Understanding the Role of Hyponitrite in Nitric Oxide Reduction

Wright

Hayton

2015

Inorg. Chem.

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“…Atomic-scale contacts may also endow the system with new properties. In covalent contacts between semiconductors or molecular radicals the hybridization of frontier orbitals may be accompanied by a strong re-distribution of charges, creating electrostatic barriers [4], or reducing the conductance of the contact [5,6].…”

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confidence: 99%

Charge Redistribution and Transport in Molecular Contacts

et al. 2015

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The forces between two single molecules brought into contact, and their connection with charge transport through the molecular junction, are studied here using non contact AFM, STM, and density functional theory simulations. A carbon monoxide molecule approaching an acetylene molecule (C_{2}H_{2}) initially feels weak attractive electrostatic forces, partly arising from charge reorganization in the presence of molecular . We find that the molecular contact is chemically passive, and protects the electron tunneling barrier from collapsing, even in the limit of repulsive forces. However, we find subtle conductance and force variations at different contacting sites along the C_{2}H_{2} molecule attributed to a weak overlap of their respective frontier orbitals.

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“…We speculate that the low temperature NO adsorption can possibly also yield more stable (NO) ) and hydroxyl-stabilized NO dimers for HT1 and HT2 N 2 O, respectively. NO reduction on metal surfaces such as Ag [34,35], Au [36], Cu [37] and Pd [38] is proposed to involve (NO) 2 dimers as intermediates. In addition, such coupled NO species in the form of hyponitrite (N 2 O 2 ) 2are also proposed as the intermediates of NO reduction cycles in biological systems employing NO reductase (NOR) [39] and flavodiiron NO reductase (FDP) [40].…”

Section: Methodsmentioning

confidence: 99%

Temperature-programmed desorption study of NO reactions on rutile TiO2(110)-1 × 1

et al. 2016

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Systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO 2 (110)-1×1 surface reveal several distinct reaction channels in a temperature range of 50-500 K. NO readily reacts on TiO 2 (110) to form N 2 O which desorbs between 50 and 200 K (LT N 2 O channels), which leaves the TiO 2 surface populated with adsorbed oxygen atoms (O a) as a byproduct of N 2 O formation. In addition, we observe simultaneous desorption peaks of NO and N 2 O at 270 K (HT1 N 2 O) and 400 K (HT2 N 2 O), respectively, both of which are attributed to reaction-limited processes. No N-derived reaction product desorbs from TiO 2 (110) surface above 500 K or higher, while the surface may be populated with O a 's and oxidized products such as NO 2 and NO 3. The adsorbate-free TiO 2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N 2 O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.

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Imaging Covalent Bonding between Two NO Molecules on Cu(110)

Cited by 33 publications

References 20 publications

Understanding the Role of Hyponitrite in Nitric Oxide Reduction

Understanding the Role of Hyponitrite in Nitric Oxide Reduction

Charge Redistribution and Transport in Molecular Contacts

Temperature-programmed desorption study of NO reactions on rutile TiO2(110)-1 × 1

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