Electron-transfer reactions are ubiquitous in chemistry and biology. The electrons' quantum nature allows their transfer across long distances. For example, the well-known harpoon mechanism, electron results Coulombic attraction between initially neutral reactants, leading to a marked increase reaction rate. Here, we present different mechanism which from reactant multiply charged cation strong repulsion that encodes electron-transfer distance kinetic energy release. Three-dimensional...

Two- and three-body Coulomb explosion dynamics of isolated ethanol dications are studied via single-photon double-ionization with ultrafast extreme-ultraviolet pulses. The measured 3-body momentum correlations obtained 3D coincidence imaging the ionic products provide evidence for several concerted sequential mechanisms: (1) a breakup mechanism, dominating channels such as CH3+ + COH+ H2; (2) dissociation in which ejection low-kinetic-energy neutral OH precedes C2H52+ → CH2+; (3) mechanism...

A homologous series of triaryl-like KITPHOS-type monophosphines containing one, two, or three bulky 12-phenyl-9,10-dihydro-9,10-ethenoanthracene (KITPHOS) units have been developed, and the influence increasing steric bulk on their efficacy as ligands in gold(I)-catalyzed carbon–heteroatom bond-forming cyclizations has investigated. Detailed solution NMR studies Ph-TRISKITPHOS, its oxide, corresponding gold(I) chloride adduct identified a conformational exchange process involving concerted...

The molecular geometries of isolated complexes in which a single molecule C2H4 or C2H2 is bound to CuCl have been determined through pure rotational spectroscopy and ab-initio calculations. C2H2···CuCl C2H4···CuCl are generated laser vaporization copper rod the presence gas sample undergoing supersonic expansion containing (or C2H4), CCl4, Ar. Results presented for five isotopologues six C2H4···CuCl. Both these adopt C(2v), T-shaped hydrocarbon binds atom its π electrons such that metal...

The Diels–Alder cycloaddition between dicyclohexylvinylphosphine oxide and anthracene or 9-methylanthracene affords the bulky electron-rich trialkyl-type dihydro-KITPHOS monophosphines 11-(dicyclohexylphosphinoyl)-12-phenyl-9,10-dihydro-9,10-ethenoanthracene 11-(dicyclohexylphosphinoyl)-9-methyl-12-phenyl-9,10-dihydro-9,10-ethenoanthracene, respectively, after reduction of corresponding oxide. Both phosphines are highly air-sensitive rapidly oxidize on silica gel during purification but have...

We study the competing mechanisms involved in Coulomb explosion of 2-propanol CH32CHOH2+ dication, formed by an ultrafast extreme ultraviolet pulse. Over 20 product channels are identified and characterized using 3D coincidence imaging ionic fragments. The momentum correlations three-body fragmentation provide evidence for a dominant sequential mechanism, starting with cleavage C-C bond, ejecting CH3+ CH3CHOH+ cations, followed secondary hydroxyethyl cation that can be delayed up to...

Photoionization can initiate structural reorganization of molecular matter and drive formation new chemical bonds. Here, we used time-resolved extreme ultraviolet (EUV) pump – EUV probe Coulomb explosion imaging carbon dioxide dimer ion $${\left({{{\rm{C}}}}{{{{\rm{O}}}}}_{2}\right)}_{2}^{+}$$ dynamics, that combined with ab initio dynamics simulations, revealed unexpected asymmetric rearrangement. We show ionization by the pulse induces rearrangement from slipped-parallel (C2h) geometry...

A new molecule C₂H₂⋯CuF has been synthesized in the gas phase by means of reaction laser-ablated metallic copper with a pulse consisting dilute mixture ethyne and sulfur hexafluoride argon.

Despite the abundance of data concerning single-photon double ionization methanol, spin state emitted electron pair has never been determined. Here we present first evidence that identifies as overwhelmingly singlet when dication forms in low-energy configurations. The experimental show while yield CH

Abstract Molecular ions are key reaction intermediates in the interstellar medium. OH + plays a central role formation of more complex chemical species and for estimating cosmic ray ionization rate astrophysical environments. Here, we use recent analysis laboratory spectrum conjunction with ab initio methods to calculate infrared ultraviolet oscillator strengths. These new strengths include branch dependent intensity corrections, arising from Herman–Wallis effect, that have not been included...

Abstract Vibration–rotation line lists for 6 LiF, 7 Li 35 Cl, 37 and Cl in the X 1 Σ + ground states have been prepared. The rovibrational energy levels calculated using potential surfaces determined by direct potential-fitting employing rotational transition frequencies of all isotopologues, required inclusion Born–Oppenheimer breakdown terms. Dipole moment functions ab initio at MRCI/aug-cc-pwCV5Z level used strength calculations. Partition temperatures up to 5000 K calculated. LiF LiCl...

Complexes of H3NCuF and H3NCuI have been synthesised in the gas phase characterized by microwave spectroscopy. The rotational spectra 4 isotopologues 5 measured 6.5-18.5 GHz frequency range using a chirped-pulse Fourier transform spectrometer. Each complex is generated from sample containing NH3 halogen-containing precursor diluted Ar. Copper introduced laser ablation solid target prior to supersonic expansion into vacuum chamber spectrum each characteristic symmetric rotor C3v geometry...

Abstract The trihydrogen ion has a central role in creating complex molecules the interstellar medium. Therefore, its formation and destruction mechanisms high photon energy environments involving organic are drawing significant experimental theoretical attention. Here, we employ combination of time‐resolved ultrafast extreme‐ultraviolet pump near‐infrared probe spectroscopy applied to deuterated CH 3 OD methanol molecule. Similar other double‐ionization studies, isotopic labeling reveals...

The H3N⋯CuCl monomer has been generated and isolated in the gas phase through laser vaporisation of a copper sample presence low concentrations NH3 CCl4 argon. resulting complex cools to rotational temperature approaching 2 K during supersonic expansion is characterised by broadband spectroscopy between 7 18.5 GHz. spectra six isotopologues are measured analysed determine rotational, B0; centrifugal distortion, DJ, DJK; nuclear quadrupole coupling constants Cu, Cl, (14)N nuclei, χaa (X)....

CO2 single-photon double photoionization, Coulomb explosion, and dissociative ionization are studied with ultrafast extreme-ultraviolet pump time-delayed near-infrared probe pulses. Kinetic energy release momentum correlations for the two-body CO+ + O+ three-body C+ O fragmentation products determined by 3D coincidence fragment imaging. The transient enhancement of ratio vs explosion events time dependence low high kinetic dissociation discussed in terms dynamics.

Carbenes of platinum and palladium, PtC3 PdC3 , were generated in the gas phase through laser vaporization a metal target presence low concentration hydrocarbon precursor undergoing supersonic expansion. Rotational spectroscopy ab initio calculations confirm that both molecules are linear. The geometry was accurately determined by fitting to experimental moments inertia twenty-six isotopologues. results consistent with proposal an autogenic isolobal relationship between O, Au(+) Pt atoms.

This paper reports the first examples of Suzuki–Miyaura cross-couplings involving aryl- and naphthylphosphonate-based boronate esters as nucleophilic partner. A systematic comparison performance biaryl-like KITPHOS- XPHOS-based systems revealed that, between them, an electronically sterically diverse range substrates can be coupled with remarkable efficiency to afford high yields corresponding biaryl heterobiaryl monophosphonates. The use ester coupling partner presents alternative...

Complexes formed between H2S and each of CuI, AgI, AuI have been isolated structurally characterised in the gas phase. The H2S⋯MI complexes (where M is metal atom) are generated through laser vaporisation a rod presence low concentration CF3I buffer argon undergoing supersonic expansion. microwave spectra six isotopologues H2S⋯CuI, H2S⋯AgI three H2S⋯AuI measured by chirped-pulse Fourier transform spectroscopy. interpreted to determine geometries for establish values structural parameters. Cs...

High-resolution infrared spectra of the symmetric top isobutane CH(CH3)3 were assigned with help ab initio calculations. The strong parallel band ν5(a1) an origin at 1396.54741(76) cm–1 and ν4(a1) mode, CH2 scissors, 1478.20363(41) rotationally analyzed. bands in C–H stretching region anharmonic calculation a local mode analysis.

The rotational spectra of H3N⋯AgI and H2O⋯AgI have been recorded between 6.5 18.5 GHz by chirped-pulse Fourier-transform microwave spectroscopy. complexes were generated through laser vaporisation a solid target silver or iodide in the presence an argon gas pulse containing low concentration Lewis base. gaseous sample subsequently undergoes supersonic expansion which results cooling vibrational motions such that weakly bound can form within expanding jet. Spectroscopic parameters determined...

A weakly-bound complex of SF6 and NH3 is generated within an expanding gas jet characterised by broadband rotational spectroscopy. The spectra isotopologues (32) ⋅⋅⋅(14) , ND3 ⋅⋅⋅(15) (34) are observed assigned to determine the spectroscopic parameters. These parameters consistent with having a C3v symmetric rotor geometry, in which nitrogen atom coordinates such that axis sub-unit aligned local C3 on sub-unit. geometry rationalized terms σ-hole interaction. ab initio calculations also...

A two force-constant model is proposed for complexes of the type B⋯MX, in which B a simple Lewis base at least C2v symmetry and MX any diatomic molecule lying along Cn axis (n ≥ 2) B. The assumes rigid subunit that force constants beyond quadratic are negligible. It leads to expressions allow, principle, determination three F11, F12, F22 associated with r(B⋯M) = r2 r(M-X) r1 internal coordinates from equilibrium centrifugal distortion DJ (e) or ΔJ (e), principal a1 a2, moments inertia. can...

Abstract A consistent set of spectroscopic constants for the a 1 Δ, d Σ + , b Π, c Φ, and f Δ states 48 Ti 16 O has been determined from analysis Π–a Π–d Φ–a Δ–a systems. Three Fourier transform emission spectra have used analysis. New bands systems fitted. The first system using is also provided. Extensive improved line positions are measured. TiO prominent in oxygen-rich cool stellar objects may be present hot-Jupiter exoplanet atmospheres.

Strongly bound complexes (CH2)3⋯MCl (M = Cu or Ag), formed by non-covalent interaction of cyclopropane and either cuprous chloride argentous chloride, have been generated in the gas phase means laser ablation copper silver metal presence supersonically expanded pulses a mixture containing small amounts carbon tetrachloride large excess argon. The rotational spectra so were detected with chirped-pulse, Fourier transform microwave spectrometer analysed to give constants Cl nuclear quadrupole...