Ion molecule reactions in the HBr + + CH 4 system: a combined experimental and theoretical study
Reactions in the system HBr++ CH4have been investigated inside a guided ion-beam apparatus under single-collision conditions and rationalized by means ofab initiomolecular dynamics.
more »
« less
- Award ID(s):
- 2144031
- PAR ID:
- 10581775
- Publisher / Repository:
- PCCP
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 26
- Issue:
- 23
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 16732 to 16746
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract Multiple bonds between boron and transition metals are known in many borylene (:BR) complexes via metal dπ→BR back‐donation, despite the electron deficiency of boron. An electron‐precise metal–boron triple bond was first observed in BiB2O−[Bi≡B−B≡O]−in which both boron atoms can be viewed as sp‐hybridized and the [B−BO]−fragment is isoelectronic to a carbyne (CR). To search for the first electron‐precise transition‐metal‐boron triple‐bond species, we have produced IrB2O−and ReB2O−and investigated them by photoelectron spectroscopy and quantum‐chemical calculations. The results allow to elucidate the structures and bonding in the two clusters. We find IrB2O−has a closed‐shell bent structure (Cs,1A′) with BO−coordinated to an Ir≡B unit, (−OB)Ir≡B, whereas ReB2O−is linear (C∞v,3Σ−) with an electron‐precise Re≡B triple bond, [Re≡B−B≡O]−. The results suggest the intriguing possibility of synthesizing compounds with electron‐precise M≡B triple bonds analogous to classical carbyne systems.more » « less
-
Abstract Nanothermometry is the study of temperature at the submicron scale with a broad range of potential applications, such as cellular studies or electronics. Molecular luminescent‐based nanothermometers offer a non‐contact means to record these temperatures with high spatial resolution and thermal sensitivity. A luminescent‐based molecular thermometer comprised of visible‐emitting Ga3+/Tb3+and Ga3+/Sm3+metallacrowns (MCs) achieved remarkable relative thermal sensitivity associated with very low temperature uncertainty ofSr=1.9 % K−1andδT<0.045 K, respectively, at 328 K, as an aqueous suspension of polystyrene nanobeads loaded with the corresponding MCs. To date, they are the ratiometric molecular nanothermometers offering the highest level of sensitivity in the physiologically relevant temperature range.more » « less
-
Abstract In a high‐resolution photoelectron imaging and theoretical study of the IrB3−cluster, two isomers were observed experimentally with electron affinities (EAs) of 1.3147(8) and 1.937(4) eV. Quantum calculations revealed two nearly degenerate isomers competing for the global minimum, both with a B3ring coordinated with the Ir atom. The isomer with the higher EA consists of a B3ring with a bridge‐bonded Ir atom (Cs,2A′), and the second isomer features a tetrahedral structure (C3v,2A1). The neutral tetrahedral structure was predicted to be considerably more stable than all other isomers. Chemical bonding analysis showed that the neutralC3visomer involves significant covalent Ir−B bonding and weak ionic bonding with charge transfer from B3to Ir, and can be viewed as an Ir–(η3‐B3+) complex. This study provides the first example of a boron‐to‐metal charge‐transfer complex and evidence of a π‐aromatic B3+ring coordinated to a transition metal.more » « less
-
We report on spectroscopic measurements on the 4f76s28S7/2∘−4f7(8S∘)6s6p(1P∘)8P5/2,7/2transitions at 466.32 nm and 462.85 nm, respectively, in neutral europium-151 and europium-153. The center of gravity frequencies for the 151 and 153 isotopes for both transitions are reported for the first time using saturated absorption spectroscopy. For the 6s6p(1P∘)8P5/2state, the center of gravity frequencies were found to be 642,894,493.3(4) MHz and 642,891,693.3(9) MHz for the 151 and 153 isotopes, respectively. The hyperfine constants for the upper state were found to beA(151)=−157.01(3)MHz,B(151)=74.5(4)MHz andA(153)=−69.43(14)MHz,B(153)=191.0(26)MHz. These hyperfine values are all consistent with previously published results except forB(151) that has a small discrepancy. The isotope shift was found to be 2799.54(20) MHz, a small discrepancy with previously published results. For the 6s6p(1P∘)8P7/2state, the center of gravity frequencies were found to be 647,708,930.6(6) MHz and 647,705,958.4(26) MHz for the 151 and 153 isotopes, respectively. The hyperfine constants for the upper state were found to beA(151)=−218.66(4)MHz,B(151)=−293.4(8)MHz andA(153)=−97.15(13)MHz,B(153)=−750(3)MHz. These values are all consistent with previously published results except forA(151) that has a small discrepancy. The isotope shift was found to be 2972.8(5) MHz, a small discrepancy with previously measured results.more » « less
An official website of the United States government

