Structure and spectroscopy of phosphorus cluster anions: Theory (simulated annealing) and experiment (photoelectron detachment)

Jones, R.; Ganteför, Gerd; Hunsicker, Stefan; Pieperhoff, Peter

doi:10.1063/1.469969

Cited by 85 publications

(108 citation statements)

References 52 publications

(49 reference statements)

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“…Nimlos et al did not cool the ions after production from a discharge and with this source have observed vibrational hot bands in other systems, 43 including an estimated vibrational temperature of 1000 K for Si 2 − . 44 Although Hunsicker et al cooled their ions with a supersonic gas expansion, they have measured a vibrational temperature of ∼580 K for P 2 − with the same ion source, 45 so hot bands may also be present in their S 3 − experiment. The higher resolution of SEVI compared to conventional PES should facilitate vibrational assignments, but Figure 1 shows that similar problems regarding vibrational temperature remain for S 3 − .…”

Section: ■ Discussionmentioning

confidence: 99%

Slow photoelectron velocity-map imaging spectroscopy of cold negative ions

Hock

Kim

Weichman

et al. 2012

The Journal of Chemical Physics

120

139

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We report high-resolution anion photoelectron spectra of thiozonide (S 3 − ) acquired by slow electron velocity-map imaging (SEVI). The ions were cryogenically cooled within an ion trap before photodetachment. We measure an electron affinity of 2.3630(9) eV, resolving discrepancies in previously reported photoelectron spectra that resulted from the presence of vibrational hot bands. The SEVI spectrum shows well-resolved, extended vibrational progressions in the symmetric stretch and bending modes of S 3 , yielding accurate frequencies for both. ■ INTRODUCTIONWith the possible exception of carbon, sulfur has more complex allotropy than any other element. 1 In addition to the numerous cyclic and polymeric forms in the solid and liquid phases, sulfur vapor is composed of the species S n (2 ≤ n ≤ 8), with trace amounts of S 9 and S 10 . 2 Aside from the diatomic S 2 , S 3 has received the most attention of these species. Its relatively small size makes it accessible to experiment and theory, and additional interest comes about because S 3 is isovalent with ozone. It has been studied by rare gas matrix IR and UV−vis spectroscopy, 3,4 resonance Raman in the gas phase, 5,6 microwave spectroscopy, 7,8 photoionization, 9 and gas-phase absorption. 10 Ab initio calculations on S 3 have focused on the question of whether the cyclic D 3h or the bent C 2v structure is the lowestenergy isomer, 11−14 finding overall agreement with experiment that the C 2v form is the stable form. High-level calculations on the structure, vibrations, and excited states of S 3 have recently been reported by Francisco et al. 15,16 In contrast to neutral S 3 , work on the S 3 − anion has largely been limited to spectroscopy in condensed phases, where it has been studied by electron paramagnetic resonance (EPR), Raman, and absorption spectroscopy. 17−19 As it is the chromophore in ultramarine pigment, 20 many of these investigations were focused on determining the properties of S 3 − in a perturbative mineral matrix or in solution. In addition, electronic absorption spectra have been measured in a cryogenic rare gas matrix. 21 Recently, the anion has been identified as the dominant form of sulfur in certain highpressure and temperature conditions approximating crustal and subduction-zone geologic fluids. 22 The new findings suggest that S 3 − may play an important role in the transport of sulfur and chalcophile metals in the earth.The neutral ← anion transition has been studied by anion photoelectron spectroscopy (PES) with resolution sufficient to resolve a progression of the ν 1 symmetric stretch. 23−25 However, the two previous studies disagreed over which peak in this progression was the vibrational origin. By assuming the anions were at the ground vibrational state, Nimlos et al. 23 obtained an electron affinity (EA) of 2.106(23) eV. Hunsicker et al. 24 found a different onset for the band, suggesting the possibility that the two experiments produced anions with different vibrational temperatures and that some of the low binding en...

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Section: ■ Discussionmentioning

confidence: 99%

Slow photoelectron velocity-map imaging spectroscopy of cold negative ions

Hock

Kim

Weichman

et al. 2012

The Journal of Chemical Physics

120

139

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“…From the enlarged view in Figure 2f&g, the structure change was similar to previously reported P 8 -anions. 74 The subsequent structure changes were also easy, with an interval of every 0.3 ps. In Figure 2h&i, a new reconstructed edge was formed by downwarping the original edge and connecting secondary edge atoms (see the Movie-S2 in SI).…”

Section: Dynamic Stability Of Phosphorene P 27 Nanoflake In Vacuummentioning

confidence: 99%

The Critical Role of Substrate in Stabilizing Phosphorene Nanoflake: A Theoretical Exploration

Gao

Zhang

2016

J. Am. Chem. Soc.

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Phosphorene, a new two-dimensional (2D) semiconductor, has received much interest due to its robust direct band gap and high charge mobility. Currently, however, phosphorene can only be produced by mechanical or liquid exfoliation, and it is still a significant challenge to directly epitaxially grow phosphorene, which greatly hinders its mass production and thus applications. In epitaxial growth, the stability of nanoscale cluster or flake on a substrate is crucial. Here, we perform ab initio energy optimizations and molecular dynamics simulations to explore the critical role of substrate on the stability of a representative phosphorene flake. Our calculations show that the stability of the phosphorene nanoflake is strongly dependent on the interaction strength between the nanoflake and substrate. Specifically, the strong interaction (0.75 eV/P atom) with Cu(111) substrate breaks up the phosphorene nanoflake, while the weak interaction (0.063 eV/P atom) with h-BN substrate fails to stabilize its 2D structure. Remarkably, we find that a substrate with a moderate interaction (about 0.35 eV/P atom) is able to stabilize the 2D characteristics of the nanoflake on a realistic time scale. Our findings here provide useful guidelines for searching suitable substrates for the directly epitaxial growth of phosphorene.

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“…The observed dominance of P 4 in phosphorus vapor and apparent instability of larger clusters provided a puzzle for several decades [6]. Only a few experiments have been performed on clusters larger than P 4 [9,11,14,15]. Recently, a wide spectrum of neutral and cationic phosphorus clusters were synthesized by visible PLA [2].…”

mentioning

confidence: 99%

“…Elemental phosphorus has been obtained in more allotropic modifications than any other element [5] and one would thus expect a variety of structural forms of P n clusters. Phosphorus clusters have been studied extensively in the last decade by theoretical approaches focused mainly on two structural families, cages (polyhedra) and chains [3,4,5,6,7,8,9,10,11,12,13]. A number of structures for P n clusters (n > 4) have been proposed as energetically more stable than tetrahedral P 4 .…”

mentioning

confidence: 99%

Phosphorus cluster production by laser ablation

et al. 2004

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Neutral and charged phosphorus clusters of a wide size range have been produced by pulsed laser ablation (PLA) in vacuum at 532, 337, and 193 nm ablating wavelengths and investigated by time-of-flight mass spectrometry. The neutral Pn clusters are even-numbered with local abundance maxima at n = 10 and 14, while the cationic and anionic clusters are preferentially odd-numbered with P + 7 , P + 21 , and P − 17 being the most abundant ions. The dominance of the magic clusters is more pronounced at 337-nm ablation that is explained by efficient direct ejection of their building blocks under these conditions. Nanocrystalline phosphorus films have been produced by PLA in ambient helium gas. One of the greatest potentials of pulsed laser ablation (PLA) is in the development of novel nanoscale materials. Recently there has been renewed interest in the study of phosphorus clusters and nanostructures as potential candidates to form fullerene-like and nanotubular materials [1,2,3,4]. Elemental phosphorus has been obtained in more allotropic modifications than any other element [5] and one would thus expect a variety of structural forms of P n clusters. Phosphorus clusters have been studied extensively in the last decade by theoretical approaches focused mainly on two structural families, cages (polyhedra) and chains [3,4,5,6,7,8,9,10,11,12,13]. A number of structures for P n clusters (n > 4) have been proposed as energetically more stable than tetrahedral P 4 . Also, the viability of phosphorus nanotubes has been predicted [1].The theoretical suggestions, however, are still not confirmed by experiment. The observed dominance of P 4 in phosphorus vapor and apparent instability of larger clusters provided a puzzle for several decades [6]. Only a few experiments have been performed on clusters larger than P 4 [9,11,14,15]. Recently, a wide spectrum of neutral and cationic phosphorus clusters were synthesized by visible PLA [2]. Different cluster distributions were observed under far-UV PLA resulting in stable hydride phosphorus clusters [16].In this work we continue our investigations on phos- * Electronic address: bulgakov@itp.nsc.ru † Electronic address: ozerov@crmcn.univ-mrs.fr phorus cluster production by PLA. Three different ablation regimes, at 532 nm, 337 nm, and 193 nm laser wavelengths, have been studied and compared with respect to P n cluster generation. Mechanisms of cluster formation under PLA conditions are discussed. In addition, the first attempt to produce nanocluster phosphorus films by PLA technique has been performed. I. EXPERIMENTThe apparatus used for laser ablation and cluster production and detection was described earlier [2,16,17]. The target (crystalline red phosphorus of 99.999% purity with respect to metals) was placed in a rotating holder in a vacuum chamber (base pressure 10 −5 Pa) and irradiated by a ns laser pulse. Three different laser systems operating at 337 nm (10 ns pulse, N 2 laser), 532 nm (13 ns, Nd:YAG laser, 2nd harmonic), and 193 nm (15 ns, ArF laser) were used for ablation. The las...

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Structure and spectroscopy of phosphorus cluster anions: Theory (simulated annealing) and experiment (photoelectron detachment)

Cited by 85 publications

References 52 publications

Slow photoelectron velocity-map imaging spectroscopy of cold negative ions

Slow photoelectron velocity-map imaging spectroscopy of cold negative ions

The Critical Role of Substrate in Stabilizing Phosphorene Nanoflake: A Theoretical Exploration

Phosphorus cluster production by laser ablation

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