Molecular Cations Research Articles

Ab initio calculation of the potential energy curves and spectroscopic properties of low-lying electronic states of CH+ molecular cation

The combined use of the MRCI-SD(T) method with the cc-pV6Z basis set has enabled us to determine the potential energy curves of the molecular cation whose fundamental state lies above the corresponding state of its neutral parent at the dissociation limit. With the accurate potential energy curves thus obtained, we have calculated spectroscopic constants which show good agreement with the experimental and other theoretical values available in the literature. To account for perturbations where necessary, spin-orbit coupling effects have been introduced. An understanding of the polarity of studied in the various electronic states is made possible by calculating the dipole moments. In addition, transition dipole moments were computed prior to the obtention of molecular parameters such as oscillator strength, Einstein coefficients, radiative probabilities and Franck–Condon factors. Overall good accuracy is observed.

Gas-phase optical absorption spectra of the indene cation (C9H8 +)

The electronic transition spectra of the indene molecular cation (In, ) in the 550–580 nm region has been measured in the gas phase in direct absorption. The spectra were experimentally recorded using sensitive cavity ring-down spectroscopy in a supersonically expanding planar plasma. Two lifetime-broadened vibronic bands are assigned to the - electronic transition system of In. A set of indicative spectroscopic parameters have been obtained from a band contour analysis of the 0 band in combination with supporting ab-initio calculations. The inferred Lorentz line width of indicates an upper state lifetime of . The laboratory data are compared to the diffuse interstellar bands (DIBs), and no matches can be found. Upper limits for In column densities in the diffuse interstellar medium have also been estimated from six sightline spectra.

Boroxine benzaldehyde complex for pharmaceutical applications probed by electron interactions.

2,4,6-Tris(4-formylphenyl)boroxine (TFPB) is a substituted boroxine containing a benzaldehyde molecule bonded to each boron atom. Boroxine cages are an emerging class of functional nanostructures used in host-guest chemistry, and benzaldehyde is a potential radiosensitizer. Reactions initiated by low-energy electrons with such complexes may dictate and bring new fundamental knowledge for biomedical and pharmaceutical applications. The electron ionization properties of TFPB are investigated using a gas-phase electron-molecule crossed beam apparatus coupled with a reflectron time-of-flight mass spectrometer in an orthogonal geometry. Ionization and threshold energies are experimentally determined by mass spectra acquisition as a function of the electron energy. The abundance of the molecular precursor cation in the mass spectrum at 70 eV is significantly lower than that of the most abundant fragment C7 H5 O+ . Twenty-nine cationic fragments with relative intensities >2% are detected and identified. The appearance energies of six fragment cations are reported, and the experimental first ionization potential is found at eV. Moreover, eight double cations are identified. The present results are supported by quantum chemical calculations based on bound state techniques, electron ionization models and thermodynamic thresholds. According to these results, the TPFB properties may combine the potential radiosensitizer effect of benzaldehyde with the stability of the boroxine ring.

Mixology of MA1-x EA x PbI3 Hybrid Perovskites: Phase Transitions, Cation Dynamics, and Photoluminescence.

Mixing molecular cations in hybrid lead halide perovskites is a highly effective approach to enhance the stability and performance of optoelectronic devices based on these compounds. In this work, we prepare and study novel mixed 3D methylammonium (MA)-ethylammonium (EA) MA1-x EA x PbI3 (x < 0.4) hybrid perovskites. We use a suite of different techniques to determine the structural phase diagram, cation dynamics, and photoluminescence properties of these compounds. Upon introduction of EA, we observe a gradual lowering of the phase-transition temperatures, indicating stabilization of the cubic phase. For mixing levels higher than 30%, we obtain a complete suppression of the low-temperature phase transition and formation of a new tetragonal phase with a different symmetry. We use broad-band dielectric spectroscopy to study the dielectric response of the mixed compounds in an extensive frequency range, which allows us to distinguish and characterize three distinct dipolar relaxation processes related to the molecular cation dynamics. We observe that mixing increases the rotation barrier of the MA cations and tunes the dielectric permittivity values. For the highest mixing levels, we observe the signatures of the dipolar glass phase formation. Our findings are supported by density functional theory calculations. Our photoluminescence measurements reveal a small change of the band gap upon mixing, indicating the suitability of these compounds for optoelectronic applications.

Electronic Terms and Oscillator Strengths of ArXe+ and KrXe+ Molecular Cations

Electronic Terms and Oscillator Strengths of ArXe+ and KrXe+ Molecular Cations

Anion Equilibria and Stability of Quaternary Phosphonium Chloroaluminate Ionic Liquids

The anion equilibria and thermal stability in a series of quaternary trialkyloctylphosphonium chloroaluminate ionic liquids are investigated qualitatively by Raman spectroscopy, broadband dielectric spectroscopy, and nuclear magnetic resonance spectroscopy. Results indicate that Lewis acidic chloroaluminate ionic liquids based upon the phosphonium cation are less stable than those based upon other molecular cations. A slow time-dependent drop in room-temperature dc ionic conductivity as well as a step drop at elevated temperatures is tentatively attributed to a reaction involving the Lewis acidic Al2Cl7 - anion and the phosphonium cations. This reaction results in significant changes in the 1H, 13C, and 31P NMR spectra, but only minor changes in the Raman spectra. Furthermore, extended time at elevated temperatures results in a significant quantity of neutral aluminum chloride sublimating from the liquid. These results demonstrate an unusual reactive instability of phosphonium-based Lewis acidic chloroaluminate ILs.

Measuring Charge Distribution of Molecular Cations by an Atomic Coulomb Probe Microscope

Imaging the charge distributions and structures of molecules and clusters will promote the understanding of the dynamics of the quantum system. Here, we report a method by using an Ar atom as a tip to probe the charge distributions of benzene (Bz) cations in gas phase. Remarkably, the measured charge distributions of Bz+ (δ H = 0.204, δ C = −0.037) and Bz2+ (δ H = 0.248, δ C = 0.0853) agree well with the calculated Mulliken distributions, and the structures of Bz2 is reconstructed by using the measured charge distributions. The structures of two Bz2 isomers (T-shaped and PD isomers) can be resolved from the measured inter-molecular potential V(R) between two Bz ions, and the structures of Bz dimer agree well with the theoretical predictions.

Chemical Characterization and Quantitation of Phenols in Fuel Extracts by Using Gas Chromatography/Methane Chemical Ionization Triple Quadrupole Mass Spectrometry

The ability to detect, characterize, and quantify phenols in aviation fuels is critical as these compounds can negatively affect the storage stability of the fuel. However, some phenols inhibit free-radical autoxidation and hence are beneficial. The development of a method based on gas chromatography coupled with positive-ion-mode methane chemical ionization/triple quadrupole mass spectrometry [GC/(methane CI) QqQ] for the characterization and quantitation of phenols in fuels is reported here. Sixteen phenols, ranging from phenol to phenols with up to three alkyl groups of different chain lengths, were studied. Natural phenols (defined as phenols without tert-butyl groups) were protonated upon methane CI, which was associated with diagnostic fragmentation. For example, upon protonation, 2-, 3-, and 4-ethylphenols fragmented via the loss of ethylene, which facilitated their distinction from the isomeric 2,4-, 2,5-, and 3,4-dimethylphenols. Furthermore, the natural phenols formed stable adducts with C2H5+ and C3H5+ ions generated from methane upon CI. In contrast, additive phenols (with one or more tert-butyl groups) were predominantly ionized via electron abstraction to yield molecular radical cations and did not form adduct ions and generated some diagnostic fragment ions, such as ions of m/z 57 (tert-butyl cation). Most of the molecular radical cations of additive phenols also exhibited a methyl radical loss, while protonated additive phenols exhibited water loss. The limit of detection and the limit of quantitation were determined to be 1.3 μM (0.33 ppm) and 4.2 μM (1.08 ppm), respectively, and the linearity of quantitation was between 5 and 160 μM. Measurements of equimolar mixtures composed of additive and natural phenols demonstrated similar (within 10%) but not identical ionization efficiencies for these two compound types. Intra- and interday measurements of the signal intensities of the phenols were highly repeatable, with average relative standard deviations of 1.7 and 5.2%, respectively. The same method was employed to successfully characterize and quantify unknown phenols in alternative and petroleum-based jet fuel extracts. The petroleum-based Jet A fuel was found to contain a 1.5 times greater concentration of phenols than the alternative fuel. Jet A contained monomethylated phenols (108 Da), while the alternative fuel did not. Several phenols with molecular weights of 122, 136, and 150 Da were detected in both Jet A and the alternative fuel. The CI mass spectra suggested that some of these phenols had multiple methyl substituents. The information that can be acquired by using the GC/(CI) QqQ method will facilitate establishing links between the chemical compositions of fuels and fuel properties. Overall, the method was found to be robust and repeatable.

Radium-containing molecular cations amenable for laser cooling

Recent successful applications of the new experimental technique to measure spectra of radium monofluoride molecules opens great prospects to searching the effects related to “new physics”. Considerable advantages in experiments for search for such effects would be provided by the abilities to trap the working molecules, their laser-coolability and also a variety of nuclear isotopes of elements in the molecule with different nuclear multipole moments.We report ab initio relativistic electronic structure calculations on a series of polyatomic molecular ions containing Ra nuclei and discuss the prospects of laser-coolability of the studied species.

Influence of Phase Transitions on Diffusive Molecular Transport Across Biological Membranes.

Phase transitions of lipid bilayer membranes should affect passive transport of molecules. While this hypothesis has been used to design drug-releasing thermosensitive liposomes, the effect has yet to be quantified. Herein, we use time-resolved second harmonic light scattering to measure transport of a molecular cation across membranes of unilamellar liposomes composed of the total lipid extract of E. coli from 9 °C to 36 °C, in which two distinct phase transitions (gel to liquid-disordered phase) have been identified. While the transport rate slowly increases with temperature as a diffusion process, dramatic jumps are observed at 14.7 °C and 27.6 °C, the known phase transitions. The transport rate constant measured as (7.3±0.8)×10-3 s-1 in the liquid-disordered phase at 36 °C is 35-times faster than (2.1±0.2)×10-4 s-1 of the gel phase at 9 °C. For the mixed-phase between these two phases, the measured rates are consistent with a structure of gel domains among a liquid-disordered bulk.

Influence of Phase Transitions on Diffusive Molecular Transport Across Biological Membranes

AbstractPhase transitions of lipid bilayer membranes should affect passive transport of molecules. While this hypothesis has been used to design drug‐releasing thermosensitive liposomes, the effect has yet to be quantified. Herein, we use time‐resolved second harmonic light scattering to measure transport of a molecular cation across membranes of unilamellar liposomes composed of the total lipid extract of E. coli from 9 °C to 36 °C, in which two distinct phase transitions (gel to liquid‐disordered phase) have been identified. While the transport rate slowly increases with temperature as a diffusion process, dramatic jumps are observed at 14.7 °C and 27.6 °C, the known phase transitions. The transport rate constant measured as (7.3±0.8)×10−3 s−1 in the liquid‐disordered phase at 36 °C is 35‐times faster than (2.1±0.2)×10−4 s−1 of the gel phase at 9 °C. For the mixed‐phase between these two phases, the measured rates are consistent with a structure of gel domains among a liquid‐disordered bulk.

Tandem Mass Spectrometric Characterization of the Molecular Radical Cations of Asphaltenes

Asphaltenes, the heaviest fraction of crude oil, are problematic for the oil industry for several reasons. For example, they have a tendency to precipitate out of oil pipelines, thus causing clogs. Further, they can foul catalysts used in refining of crude oil. However, the lack of knowledge on the exact molecular structures of asphaltenes has long prevented addressing the above problems and also hindered finding financially beneficial uses for asphaltenes. This paper focuses on recent advances on the structural characterization of the molecular radical cations of asphaltenes based on collision-activated dissociation (CAD) experiments performed using linear quadrupole ion trap mass spectrometers coupled to an Orbitrap detector. Stable molecular radical cations are readily generated from asphaltenes upon atmospheric pressure chemical ionization (APCI) when using CS2 as the solvent because this solvent cannot transfer a proton to analytes. MS2–MS5 experiments based on ion-source CAD (ISCAD), ion-trap CAD (ITCAD), and/or medium-energy CAD (MCAD) were explored for the structural characterization of these molecular radical cations by using model compounds. Energy-resolved MCAD experiments were identified as the most useful experiments because they provide substantially more structural information for the radical cations than the other CAD experiments mentioned above. In some MSn experiments, MSn–1 was first performed in the ion trap, followed by isolation of a desired ion in the ion trap and transfer into the MCAD collision cell, wherein it was subjected to energy-resolved MCAD followed by high-resolution detection of the fragment ions. The various CAD experiments were used to obtain information on compounds in asphaltene samples with different origins, such as the aliphatic carbon content, molecular weight distributions (MWDs), average molecular weight, number of aromatic carbon atoms, number of aromatic rings in the core, and relative abundances of single-core and multicore compounds.

Single-Crystal to Single-Crystal Addition of H2 to [Ir(iPr-PONOP)(propene)][BArF 4] and Comparison Between Solid-State and Solution Reactivity.

The reactivity of the Ir(I) PONOP pincer complex [Ir(iPr-PONOP)(η2-propene)][BArF 4], 6, [iPr-PONOP = 2,6-(iPr2PO)2C6H3N, ArF = 3,5-(CF3)2C6H3] was studied in solution and the solid state, both experimentally, using molecular density functional theory (DFT) and periodic-DFT computational methods, as well as in situ single-crystal to single-crystal (SC-SC) techniques. Complex 6 is synthesized in solution from sequential addition of H2 and propene, and then the application of vacuum, to [Ir(iPr-PONOP)(η2-COD)][BArF 4], 1, a reaction manifold that proceeds via the Ir(III) dihydrogen/dihydride complex [Ir(iPr-PONOP)(H2)H2][BArF 4], 2, and the Ir(III) dihydride propene complex [Ir(iPr-PONOP)(η2-propene)H2][BArF 4], 7, respectively. In solution (CD2Cl2) 6 undergoes rapid reaction with H2 to form dihydride 7 and then a slow (3 d) onward reaction to give dihydrogen/dihydride 2 and propane. DFT calculations on the molecular cation in solution support this slow, but productive, reaction, with a calculated barrier to rate-limiting propene migratory insertion of 24.8 kcal/mol. In the solid state single-crystals of 6 also form complex 7 on addition of H2 in an SC-SC reaction, but unlike in solution the onward reaction (i.e., insertion) does not occur, as confirmed by labeling studies using D2. The solid-state structure of 7 reveals that, on addition of H2 to 6, the PONOP ligand moves by 90° within a cavity of [BArF 4]- anions rather than the alkene moving. Periodic DFT calculations support the higher barrier to insertion in the solid state (ΔG ‡ = 26.0 kcal/mol), demonstrating that the single-crystal environment gates onward reactivity compared to solution. H2 addition to 6 to form 7 is reversible in both solution and the solid state, but in the latter crystallinity is lost. A rare example of a sigma amine-borane pincer complex, [Ir(iPr-PONOP)H2(η1-H3B·NMe3)][BArF 4], 5, is also reported as part of these studies.

Complexation of Astatine(III) with Ketones: Roles of NO3- Counterion and Exploration of Possible Binding Modes.

Ketones have been proven effective in extracting astatine(III) from aqueous solvents. Previous theoretical studies suggested a mechanism where the "sp2" lone pair on the carbonyl oxygen donates electron density into the π system of the AtO+ molecular cation to form a dative-type bond. In this study, co-extraction of NO3- as AtO(NO3)·(O═CR1R2) species into the organic phase appears to be a key factor. Adjusting the electronic properties of the ketone, by having an aryl group instead of an alkyl group in the alpha position of the ketone, increased the electron density on C═O, increased the bond strength between the ketone and AtO+, and in turn increased the extraction of 211At into the organic phase. Extraction with diketones shows dependence on the bridging distance between the two carbonyl moieties, where a C3 or longer bridge results in a 10-fold increase in extraction into the organic phase. DFT calculations show the longer bridge allows for the chelation of AtO(NO3) by either the second carbonyl or the phenyl ring.

Toward Detection of FeH+ in the Interstellar Medium: Infrared Multiple Photon Dissociation Spectroscopy of Ar2FeH.

The iron hydride molecular cation FeH+ is expected to be present in the interstellar medium. Because of the lack of laboratory data, it is yet to be identified in spectrally resolved astronomic observations. As a benchmark for computational predictions and to guide an experimental search for the ro-vibrational lines of FeH+, we performed infrared multiple photon dissociation (IRMPD) spectroscopy of FeH+ tagged with two argon atoms. The Fe–H stretching mode in Ar2FeH+ is observed at 1860 cm–1. Combination bands of the Fe–H stretch with the two Fe–H bending and the asymmetric Fe–Ar stretching modes are observed at 2012 cm–1, 2054 cm–1, and 2078 cm–1. Quantum chemical calculations show that the molecule has C2v symmetry. The Ar–Fe–Ar bending mode at 46 cm–1 is significantly populated at the temperature of the experiment, causing thermal broadening of the Fe–H stretch and its redshift with increasing internal energy.

A Coupled EXAFS-Molecular Dynamics Study on PuO2+ and NpO2+ Hydration: The Importance of Electron Correlation in Force-Field Building.

The physicochemical properties of the monovalent actinyl cations, PuO2+ and NpO2+, in water have been studied by means of classical molecular dynamic simulations. A specific set of cation-water intermolecular potentials based on ab initio potential energy surfaces has been built on the basis of the hydrated ion concept. The TIP4P water model was adopted. Given the paramagnetic character of these actinyls, the cation–water interaction energies were computed from highly correlated wave functions using the NEVPT2 method. It is shown that the multideterminantal character of the wave function has a relevant effect on the main distances of the hydrated molecular cations. Several structural, dynamical, and energetic properties of the aqueous solutions have been obtained and analyzed. Structural RDF analysis gives An–Oyl distances of 1.82 and 1.84 Å and An–O(water) distances of 2.51 and 2.53 Å for PuO2+ and NpO2+ in water, respectively. Experimental EXAFS spectra from dilute aqueous solutions of PuO2+ and NpO2+ are revisited and analyzed, assuming tetra- and pentahydration of the actinyl cations. Simulated EXAFS spectra have been computed from the snapshots of the MD simulations. Good agreement with the experimental information available is found. The global analysis leads us to conclude that both PuO2+ and NpO2+ cations in water are stable pentahydrated aqua ions.

Force Field Parameterization of Actinyl Molecular Cations Using the 12-6-4 Model.

In this work, a set of 12-6-4 force fields (FFs) parameters were developed for the actinyl molecular cations, AnO2n+ (n = 1, 2), from uranium to plutonium for classical molecular dynamics (MD) for four water models: TIP3P, SPC/E, OPC3, and TIP4Pew. Such a non-bonded potential model taking into account the induced dipole between the metallic center and the surrounding molecules has shown better performances for various cations than the classic 12-6 non-bonded potentials. The parametrization method proposed elsewhere for metallic cations has been extended to these molecular cations. In contrast to the actinyl 12-6 FFs from the literature, the new models reproduce correctly both solvation and thermodynamic properties, thanks to the inclusion of the induced dipole term (C4). The transferability of such force fields was assessed by performing MD simulations of carbonato actinyl species, which are highly implicated in actinide migration or actinide extraction from seawater. A highly satisfying agreement was found when comparing the EXAFS signals computed from our MD simulation to the experimental ones. The set of FFs developed here opens new possibilities for the study of actinide chemistry.

Spectroscopy and rovibrational cooling of AuF and its cation

The feasibility of laser cooling of AuF molecule and its cation are investigated from vibrational and rotational perspectives. The spectroscopy of AuF molecule and AuF+ molecular cation are obtained by the method of multireference configuration interaction plus Davidson correction (MRCI + Q) and spin–orbit coupling (SOC) effect. On account of the accurate molecular spectroscopy and the transition dipole moment, the Franck-Condon factors and radiative lifetimes of AuF molecule and AuF+ molecular cation are calculated. Comparing the criterias of laser cooling candidate molecules, the AuF is an excellent candidate for laser cooling and while AuF+ is not sutable. The b3Π0+ ↔ Χ1Σ+0+ transition of AuF is selected for laser cooling and an optical cycling scheme is proposed. The scheme possesses highly diagonally Franck-Condon factors and the scattered photons achieve ∼ 104. Furthermore, the rotational transition analysis is also included in our work and found that its Franck Condon factors and Einstein coefficients are undistorted. Our work could provide theoretical support and accelerate the laser cooling of AuF molecules in experiments.

Fast fluoride ion conduction of NH4(Mg1-xLix)F3-x and (NH4)2(Mg1-xLix)F4-x assisted by molecular cations

Aiming development of the fast anion conductors, we proposed a new material design using flexible molecular cation as a host cation, and demonstrated it with fluoride ion conduction in NH4MgF3 and (NH4)2MgF4 based materials. Dominant fluoride ion conduction with relatively high conductivities of 4.8 × 10–5 S cm−1 and 8.4 × 10–6 S cm−1 were achieved at 323 K in (NH4)2(Mg0.85Li0.15)F3.85 and NH4(Mg0.9Li0.1)F2.9, respectively. It is implied that the molecular cation in the host lattice can assist the anion conduction. Our findings suggest molecular cation-containing compounds can be attractive material groups for fast anion conductors.

Preliminary results of positive ion mass spectrometry based on a 2.45 GHz ECR ion source and a non-metallic gas target

Positive-ion mass spectrometry (PIMS) is a positive-to-negative ion conversion metrology that just operated on the opposite of traditional accelerator mass spectrometry (AMS) on high-precision radiocarbon dating. With a higher efficient simple structure plasma ion sources instead of AMS sputter ion sources, lower ion energy (tens keV) in place of MeV, and limited footprint facility, PIMS will be a powerful competitor to AMS in the future. To precisely measure 14C, interference of molecular isobars (such as 12CH2, 13CH) will be eliminated with higher charged ions (charge state ≥ 3; molecular cations 12CH2 2+ is metastable, can be eliminated by higher stripping pressure.), nitrogen will be eliminated inside the charge-exchange cell (CXC) through charge exchanging with target gas. To demonstrate the probability of PIMS with a 2.45 GHz ECR ion source, an experiment was launched at Peking University (PKU). A compact permanent magnet 2.45 GHz ECR ion source is designed to produce carbon ions from CO2. A CXC unit was installed after the extraction system and ethylene is chosen as charge exchange gas. Preliminary experiments prove that more than hundreds of microamp of C2+ beam can be produced with this ECR source. By injecting ethylene into CXC, several microamp C- beam was detected and the C2+ ions charge exchange efficiency to C- ions can reach close to 5%.