Synthesis, Characterization, and Computational Studies on Gallium(III) and Iron(III) Complexes with a Pentadentate Macrocyclic bis-Phosphinate Chelator and Their Investigation As Molecular Scaffolds for 18F Binding.

With the aim of obtaining improved molecular scaffolds for 18F binding to use in PET imaging, gallium(III) and iron(III) complexes with a macrocyclic bis-phosphinate chelator have been synthesized and their properties, including their fluoride binding ability, investigated. Reaction of Bn-tacn (1-benzyl-1,4,7-triazacyclononane) with paraformaldehyde and PhP(OR)2 (R = Me or Et) in refluxing THF, followed by acid hydrolysis, yields the macrocyclic bis(phosphinic acid) derivative, H2(Bn-NODP) (1-benzyl-4,7-phenylphosphinic acid-1,4,7-triazacyclononane), which is isolated as its protonated form, H2(Bn-NODP)·2HCl·4H2O, at low pH (HClaq), its disodium salt, Na2(Bn-NODP)·5H2O at pH 12 (NaOHaq), or the neutral H2(Bn-NODP) under mildly basic conditions (Et3N). A crystal structure of H2(Bn-NODP)·2HCl·H2O confirmed the ligand's identity. The mononuclear [GaCl(Bn-NODP)] complex was prepared by treatment of either the HCl or sodium salt with Ga(NO3)3·9H2O or GaCl3, while treatment of H2(Bn-NODP)·2HCl·4H2O with FeCl3 in aqueous HCl gives [FeCl(Bn-NODP)]. The addition of 1 mol. equiv of aqueous KF to these chloro complexes readily forms the [MF(Bn-NODP)] analogues. Spectroscopic analysis on these complexes confirms pentadentate coordination of the doubly deprotonated (bis-phosphinate) macrocycle via its N3O2 donor set, with the halide ligand completing a distorted octahedral geometry; this is further confirmed through a crystal structure analysis on [GaF(Bn-NODP)]·4H2O. The complex adopts the geometric isomer in which the phosphinate arms are coordinated unsymmetrically (isomer 1) and with the stereochemistry of the three N atoms of the tacn ring in the RRS configuration, denoted (N)RRS, and the phosphinate groups in the RR stereochemistry, denoted (P)RR, (isomer 1/RR), together with its (N)SSR (P)SS enantiomer. The greater thermodynamic stability of isomer 1/RR over the other possible isomers is also indicated by density functional theory (DFT) calculations. Radiofluorination experiments on the [MCl(Bn-NODP)] complexes in partially aqueous MeCN/NaOAcaq (Ga) or EtOH (Ga or Fe; i.e. without buffer) with 18F- target water at 80 °C/10 min lead to high radiochemical incorporation (radiochemical yields 60-80% at 1 mg/mL, or ∼1.5 µM, concentration of the precursor). While the [Fe18F(n-NODP)] is unstable (loss of 18F-) in both H2O/EtOH and PBS/EtOH (PBS = phosphate buffered saline), the [Ga18F(Bn-NODP)] radioproduct shows excellent stability, RCP = 99% at t = 4 h (RCP = radiochemical purity) when formulated in 90%:10% H2O/EtOH and ca. 95% RCP over 4 h when formulated in 90%:10% PBS/EtOH. This indicates that the new "GaIII(Bn-NODP)" moiety is a considerably superior fluoride binding scaffold than the previously reported [Ga18F(Bn-NODA)] (Bn-NODA = 1-benzyl-4,7-dicarboxylate-1,4,7-triazacyclononane), which undergoes rapid and complete hydrolysis in PBS/EtOH (refer to Chem. Eur. J. 2015, 21, 4688-4694).

A study of the thermodynamics and mechanisms of the atmospherically relevant reaction dimethyl sulphide (DMS) with atomic chlorine (Cl) in the absence and presence of water, using electronic structure methods.

The thermodynamics and mechanisms of the atmospherically relevant reaction dimethyl sulphide (DMS) + atomic chlorine (Cl) were investigated in the absence and presence of a single water molecule, using electronic structure methods. Stationary points on each reaction surface were located using density functional theory (DFT) with the M06-2X functional with aug-cc-pVDZ (aVDZ) and aug-cc-pVTZ (aVTZ) basis sets. Then fixed point calculations were carried out using the UM06-2X/aVTZ optimised stationary point geometries, with aug-cc-pVnZ basis sets (n = T and Q), using the coupled cluster method [CCSD(T)], as well as the domain-based local pair natural orbitals coupled cluster [DLPNO-UCCSD(T)] approach. Four reaction channels are possible, formation of (A) CH3SCH2 + HCl, (B) CH3S + CH3Cl, (C) CH3SCl + CH3, and (C') CH3S(Cl)CH3. The results show that, in the absence of water, channels A and C' are the dominant channels. In the presence of water, the calculations show that the reaction mechanisms for A and C formation change significantly. Channel A occurs via submerged TSs and is expected to be rapid. Channel B occurs via TSs which present significant energy barriers indicating that this channel is not significant in the presence of water relative to CH3SCH2 + HCl and DMS·Cl adduct formation, as is the case in the absence of water. Channel C was not considered as it is endothermic in the absence of water. In the presence of water, pathways which proceed via (a) DMS·H2O + Cl, (b) Cl·H2O + DMS and (c) DMS·Cl + H2O were considered. It was found that under tropospheric conditions, reactions via pathway (b) are of minor importance relative to those that proceed via pathways (a) and (c). This study has shown that water changes the mechanisms of the DMS + Cl reactions significantly but the presence of water is not expected to affect the overall reaction rate coefficient under atmospheric conditions as the DMS + Cl reaction has a rate coefficient at room temperature close to the collisional limit.

Neutral and Cationic Complexes of Silicon(IV) Halides with Phosphine Ligands.

The reaction of SiI4 and PMe3 in n-hexane produced the yellow salt, [SiI3(PMe3)2]I, confirmed from its X-ray structure, containing a trigonal bipyramidal cation with trans-phosphines. This contrasts with the six-coordination found in (the known) trans-[SiX4(PMe3)2] (X = Cl, Br) complexes. The diphosphines o-C6H4(PMe2)2 and Et2P(CH2)2PEt2 form six-coordinate cis-[SiI4(diphosphine)], which were also characterized by X-ray crystallography, multinuclear NMR, and IR spectroscopy. Reaction of trans-[SiX4(PMe3)2] (X = Cl, Br) with Na[BArF] (BArF = [B{3,5-(CF3)2C6H3}4]) produced five-coordinate [SiX3(PMe3)2][BArF], but while Me3SiO3SCF3 also abstracted chloride from trans-[SiCl4(PMe3)2], the reaction products were six-coordinate complexes [SiCl3(PMe3)2(OTf)] and [SiCl2(PMe3)2(OTf)2] with the triflate coordinated. X-ray crystal structures were obtained for [SiCl3(PMe3)2][BArF] and [SiCl2(PMe3)2(OTf)2]. The charge distribution across the silicon species was also examined by natural bond orbital (NBO) analyses of the computed density functional theory (DFT) wavefunctions. For the [SiX4(PMe3)2] and [SiX3(PMe3)2]+ complexes, the positive charge on Si decreases and the negative charge on X decreases going from X = F to X = I. Upon going from [SiX4(PMe3)2] to [SiX3(PMe3)2]+, i.e., removal of X-, there is an increase in positive charge on Si and a decrease in negative charge on the X centers (except for the case X = F). The positive charge on P shows a slight decrease.

An experimental and theoretical characterization of the electronic structure of doubly ionised disulfur.

Using time-of-flight multiple electron and ion coincidence techniques in combination with a helium gas discharge lamp and synchrotron radiation, the double ionisation spectrum of disulfur (S[Formula: see text]) and the subsequent fragmentation dynamics of its dication are investigated. The S[Formula: see text] sample was produced by heating mercury sulfide (HgS), whose vapour at a suitably chosen temperature consists primarily of two constituents: S[Formula: see text] and atomic Hg. A multi-particle-coincidence technique is thus particularly useful for retrieving spectra of S[Formula: see text] from ionisation of the mixed vapour. The results obtained are compared with detailed calculations of the electronic structure and potential energy curves of S[Formula: see text] which are also presented. These computations are carried out using configuration interaction methodology. The experimental results are interpreted with and strongly supported by the computational results.

Single photon double and triple ionization of allene.

Double and triple ionization of allene are investigated using electron-electron, ion-ion, electron-electron-ion and electron-electron-ion-ion (ee, ii, eei, eeii) coincidence spectroscopies at selected photon energies. The results provide supporting evidence for a previously proposed roaming mechanism in H3+ formation by double ionization. The lowest vertical double ionization energy is found to be 27.9 eV, while adiabatic double ionization is not accessed by vertical ionization at the neutral geometry. The triple ionization energy is found to be close to 50 eV in agreement with theoretical predictions. The doubly charged parent ion is stable up to about 2 eV above the threshold, after which dissociations by charge separation and by double charge retention occur with comparable intensities. Fragmentation to H+ + C3H3+ starts immediately above the threshold as a slow (metastable) decay with 130.5 ± 9.9 ns mean lifetime.

Pyramidal Dicationic Ge(II) Complexes with Homoleptic Neutral Pnictine Coordination: A Combined Experimental and Density Functional Theory Study.

An unusual series of Ge(II) dicationic species with homoleptic phosphine and arsine coordination, [Ge(L)][OTf]2, L = 3 × PMe3, triphos (MeC(CH2PPh2)3), triars (MeC(CH2AsMe2)3), or κ3-tetraphos (P(CH2CH2PPh2)3) (OTf- = O3SCF3-) have been prepared by reaction of [GeCl2(dioxane)] with L and 2 mol equiv of Me3SiOTf in anhydrous CH2Cl2 (or MeCN for L = triars, triphos). X-ray crystal structures are reported for [Ge(PMe3)3][OTf]2, [Ge(triars)][OTf]2, and [Ge(κ3-tetraphos)][OTf]2, confirming homoleptic P3- or As3-coordination at Ge(II) in each case and with the discrete OTf- anions providing a charge balance. The Ge-P/As bond lengths are significantly shorter than those in neutral germanium(II) dihalide complexes with diphosphine or diarsine coordination. Solution NMR spectroscopic data indicate that the complexes are labile in solution. Using excess AsMe3 and [GeCl2(dioxane)] gives only the neutral product, [Ge(AsMe2)2(OTf)2], the crystal structure of which shows four coordination at Ge(II), via two As donor atoms and an O atom from two κ1-OTf- ligands; further weak, long-range intermolecular interactions give a chain polymer. The electronic structure of the [Ge(PMe3)3]2+ dication has been investigated using density functional theory (DFT) calculations. The computed geometrical parameters for this dication are in good agreement with the experimental X-ray crystallographic values in [Ge(PMe3)3][OTf]2. The results also indicate that the pyramidal arrangement of the [Ge(PMe3)3]2+ (computed P-Ge-P angle 96.8° at the B3LYP-D3 level) arises from a balance between electronic energy (Eelec) contributions, which favor a lower P-Ge-P angle, and nuclear-nuclear contributions (Enn), which favor a higher P-Ge-P angle, to the total energy (ETOT). An Atoms in Molecules (AIM) analysis reveals that one reason why Eelec decreases as the P-Ge-P angle decreases is because of C···H and H···H interactions between atoms on different CH3 groups. The stability of the [Ge(PMe3)3]2+ dication is enhanced by the distribution of a significant part of the positive charge on Ge2+ to the atomic centers of the PMe3 ligands. Similar results were obtained for [Ge(AsMe3)3][OTf]2, showing the tris-AsMe3 complex to be less stable compared to the PMe3 analogue. Related calculations were also performed for the neutral [Ge(PMe3)2(OTf)2] and [Ge(AsMe3)2(OTf)2] complexes.

Comment on "Impact of water on the BrO + HO2 gas-phase reaction: mechanism, kinetics and products" by N. T. Tsona, S. Tang and L. Du, Phys. Chem. Chem. Phys., 2019, 21, 20296.

The reaction, BrO + HO2 → HOBr + O2, is exothermic and can produce O2 in both its ground state (X[combining tilde]3∑g-) and its first excited state (ã1Δg). As a result, this reaction can proceed on both a singlet and a triplet potential energy surface. Recently, Tsona, Tang and Du published a paper entitled "Impact of water on the BrO + HO2 gas-phase reaction: mechanism, kinetics and products (Phys. Chem. Chem. Phys. 2019, 21, 20296-203072). The results of this work showed significant differences from those published earlier on this reaction by Chow et al. (Phys. Chem. Chem. Phys. 2016, 18, 30554-30569). Further calculations performed in this present work, combined with higher level calculations published by Chow et al. (Phys. Chem. Chem. Phys. 2016, 18, 30554-30569), demonstrate that the work of Tsona et al. is flawed because the integration grid size used in their lowest singlet and triplet calculations is too small, and a closed-shell wavefunction, rather than an open-shell wavefunction, has been used for the singlet surface. The major conclusion in the work of Tsona et al. that the lowest singlet and triplet channels are barrierless is shown to be incorrect. Also, the computed rate coefficients of Tsona et al. showed a positive temperature dependence, which is inconsistent with the experimentally observed negative temperature dependence, whereas the singlet rate coefficients computed by Chow et al. (Phys. Chem. Chem. Phys. 2016, 18, 30554-30569) showed a negative temperature dependence consistent with experiment.

Spectroscopy on the wing: Investigating possible differences in protein secondary structures in feather shafts of birds using Raman spectroscopy.

The central shaft of a bird's flight feather bears most of the aerodynamic load during flight and exhibits some remarkable mechanical properties. The shaft comprises two parts, the calamus and the rachis. The calamus is at the base of the shaft, while the rachis is the longer upper part which supports the vanes. The shaft is composed of a fibrous outer cortex, and an inner foam-like core. Recent nanoindentation experiments have indicated that reduced modulus values, Er, for the inner and outer regions of the cortex can vary, with the Er values of the inner region slightly greater than those of the outer region. In this work, Raman spectroscopy is used to investigate the protein secondary structures in the inner and outer regions of the feather cortex. Analysis of the Amide I region of Raman spectra taken from four birds (Swan, Gull, Mallard and Kestrel) shows that the ß-sheet structural component decreases between the inner and outer region, relative to the protein side-chain components. This finding is consistent with the proposal that Er values are greater in the inner region than the outer region. This work has shown that Raman spectroscopy can be used effectively to study the change in protein secondary structure between the inner and outer regions of a feather shaft.

Tertiary Phosphine and Arsine Complexes of Phosphorus Pentafluoride: Synthesis, Properties, and Electronic Structures.

The reaction of PMe3 or PPh3 with PF5 in anhydrous CH2Cl2 or hexane forms the white, moisture-sensitive complexes [PF5(PR3)] (R = Me, Ph). Similar reactions involving the diphosphines o-C6H4(PR2)2 afford the complexes [PF4{o-C6H4(PR2)2}][PF6]. The X-ray structures of [PF5(PR3)] and [PF4{o-C6H4(PMe2)2}][PF6] show pseudo-octahedral fluorophosphorus centers. Multinuclear NMR spectra (1H, 19F{1H}, 31P{1H}) show that in solution in CH2Cl2/CD2Cl2 the structures determined crystallographically are the only species present for [PF5(PMe3)] and [PF4{o-C6H4(PMe2)2}][PF6] but that [PF5(PPh3)] and [PF4{o-C6H4(PPh2)2}][PF6] exhibit reversible dissociation of the phosphine at ambient temperatures, although exchange slows at low temperatures. The complex 19F{1H} and 31P{1H} NMR spectra have been analyzed, including those of the cation [PF4{o-C6H4(PMe2)2}]+, which is a second-order AA'XX'B2M spin system. The unstable [PF5(AsMe3)], which decomposes in a few hours at ambient temperatures, has also been isolated and spectroscopically characterized; neither AsPh3 nor SbEt3 forms similar complexes. The electronic structures of the PF5 complexes have been explored by DFT calculations. The DFT optimized geometries for [PF5(PMe3)], [PF5(PPh3)], and [PF4{o-C6H4(PMe2)2}]+ are in good agreement with their respective crystal structure geometries. DFT calculations on the PF5-L complexes reveal the P-L bond strength falls with L in the order PMe3 > PPh3 > AsMe3, consistent with the experimentally observed stabilities, and in the PF5-L complexes, electron transfer from L to PF5 on forming these complexes also follows the order PMe3 > PPh3 ≈ AsMe3.

Photoionization studies of reactive intermediates using synchrotron radiation.

Photoionization of reactive intermediates with synchrotron radiation has reached a sufficiently advanced stage of development that it can now contribute to a number of areas in gas-phase chemistry and physics. These include the detection and spectroscopic study of reactive intermediates produced by bimolecular reactions, photolysis, pyrolysis or discharge sources, and the monitoring of reactive intermediates in situ in environments such as flames. This review summarises advances in the study of reactive intermediates with synchrotron radiation using photoelectron spectroscopy (PES) and constant-ionic-state (CIS) methods with angular resolution, and threshold photoelectron spectroscopy (TPES), taking examples mainly from the recent work of the Southampton group. The aim is to focus on the main information to be obtained from the examples considered. As future research in this area also involves photoelectron-photoion coincidence (PEPICO) and threshold photoelectron-photoion coincidence (TPEPICO) spectroscopy, these methods are also described and previous related work on reactive intermediates with these techniques is summarised. The advantages of using PEPICO and TPEPICO to complement and extend TPES and angularly resolved PES and CIS studies on reactive intermediates are highlighted.

A study of the Group 1 metal tetra-aza macrocyclic complexes [M(Me4cyclen)(L)]+ using electronic structure calculations.

Metal-cyclen complexes have a number of important applications. However, the coordination chemistry between metal ions and cyclen-based macrocycles is much less well studied compared to their metal ion-crown ether analogues. This work, which makes a contribution to address this imbalance by studying complex ions of the type [M(Me4cyclen)(L)]+, was initiated by results of an experimental study which prepared some Group 1 metal cyclen complexes, namely [Li(Me4cyclen)(H2O)][BArF] and [Na(Me4cyclen)(THF)][BArF] and obtained their X-ray crystal structures [J. M. Dyke, W. Levason, M. E. Light, D. Pugh, G. Reid, H. Bhakhoa, P. Ramasami, and L. Rhyman, Dalton Trans., 2015, 44, 13853]. The lowest [M(Me4cyclen)(L)]+ minimum energy structures (M = Li, Na, K, and L = H2O, THF, DEE, MeOH, DCM) are studied using density functional theory (DFT) calculations. The geometry of each [M(Me4cyclen)(L)]+ structure and, in particular, the conformation of L are found to be mainly governed by steric hindrance which decreases as the size of the ionic radius increases from Li+ → Na+ → K+. Good agreement of computed geometrical parameters of [Li(Me4cyclen)(H2O)]+ and [Na(Me4cyclen)(THF)]+ with the corresponding geometrical parameters derived from the crystal structures [Li(Me4cyclen)(H2O)]+[BArF]- and [Na(Me4cyclen)(THF)]+[BArF]- is obtained. Bonding analysis indicates that the stability of the [M(Me4cyclen)(L)]+ structures originates mainly from ionic interaction between the Me4cyclen/L ligands and the M+ centres. The experimental observation that [M(Me4cyclen)(L)]+[BArF]- complexes could be prepared in crystalline form for M+ = Li+ and Na+, but that experiments aimed at synthesising the corresponding K+, Rb+, and Cs+ complexes failed resulting in formation of [Me4cyclenH][BArF] is investigated using DFT and explicitly correlated calculations, and explained by considering production of [Me4cyclenH]+ by a hydrolysis reaction, involving traces of water, which competes with [M(Me4cyclen)(L)]+ formation. [Me4cyclenH]+ formation dominates for M+ = K+, Rb+, and Cs+ whereas formation of [M(Me4cyclen)(L)]+ is energetically favoured for M+ = Li+ and Na+. The results indicate that the number and type of ligands, play a key role in stabilising the [M(Me4cyclen)]+ complexes and it is hoped that this work will encourage experimentalists to prepare and characterise other [M(Me4cyclen)(L)]+ complexes.

The Atmospherically Important Reaction of Hydroxyl Radicals with Methyl Nitrate: A Theoretical Study Involving the Calculation of Reaction Mechanisms, Enthalpies, Activation Energies, and Rate Coefficients.

A theoretical study, involving the calculation of reaction enthalpies, activation energies, mechanisms, and rate coefficients, was made of the reaction of hydroxyl radicals with methyl nitrate, an important process for methyl nitrate removal in the earth's atmosphere. Four reaction channels were considered: formation of H2O + CH2ONO2, CH3OOH + NO2, CH3OH + NO3, and CH3O + HNO3. For all channels, geometry optimization and frequency calculations were performed at the M06-2X/6-31+G** level, while relative energies were improved at the UCCSD(T*)-F12/CBS level. The major channel is found to be the H abstraction channel, to give the products H2O + CH2ONO2. The reaction enthalpy (ΔH298 KRX) of this channel is computed as -17.90 kcal mol-1. Although the other reaction channels are also exothermic, their reaction barriers are high (>24 kcal mol-1), and therefore these reactions do not contribute to the overall rate coefficient in the temperature range considered (200-400 K). Pathways via three transition states were identified for the H abstraction channel. Rate coefficients were calculated for these pathways at various levels of variational transition state theory including tunneling. The results obtained are used to distinguish between two sets of experimental rate coefficients, measured in the temperature range of 200-400 K, one of which is approximately an order of magnitude greater than the other. This comparison, as well as the temperature dependence of the computed rate coefficients, shows that the lower experimental values are favored. The implications of the results to atmospheric chemistry are discussed.

Direct Measurements of Unimolecular and Bimolecular Reaction Kinetics of the Criegee Intermediate (CH3)2COO.

The Criegee intermediate acetone oxide, (CH3)2COO, is formed by laser photolysis of 2,2-diiodopropane in the presence of O2 and characterized by synchrotron photoionization mass spectrometry and by cavity ring-down ultraviolet absorption spectroscopy. The rate coefficient of the reaction of the Criegee intermediate with SO2 was measured using photoionization mass spectrometry and pseudo-first-order methods to be (7.3 ± 0.5) × 10-11 cm3 s-1 at 298 K and 4 Torr and (1.5 ± 0.5) × 10-10 cm3 s-1 at 298 K and 10 Torr (He buffer). These values are similar to directly measured rate coefficients of anti-CH3CHOO with SO2, and in good agreement with recent UV absorption measurements. The measurement of this reaction at 293 K and slightly higher pressures (between 10 and 100 Torr) in N2 from cavity ring-down decay of the ultraviolet absorption of (CH3)2COO yielded even larger rate coefficients, in the range (1.84 ± 0.12) × 10-10 to (2.29 ± 0.08) × 10-10 cm3 s-1. Photoionization mass spectrometry measurements with deuterated acetone oxide at 4 Torr show an inverse deuterium kinetic isotope effect, kH/kD = (0.53 ± 0.06), for reactions with SO2, which may be consistent with recent suggestions that the formation of an association complex affects the rate coefficient. The reaction of (CD3)2COO with NO2 has a rate coefficient at 298 K and 4 Torr of (2.1 ± 0.5) × 10-12 cm3 s-1 (measured with photoionization mass spectrometry), again similar to rate for the reaction of anti-CH3CHOO with NO2. Cavity ring-down measurements of the acetone oxide removal without added reagents display a combination of first- and second-order decay kinetics, which can be deconvolved to derive values for both the self-reaction of (CH3)2COO and its unimolecular thermal decay. The inferred unimolecular decay rate coefficient at 293 K, (305 ± 70) s-1, is similar to determinations from ozonolysis. The present measurements confirm the large rate coefficient for reaction of (CH3)2COO with SO2 and the small rate coefficient for its reaction with water. Product measurements of the reactions of (CH3)2COO with NO2 and with SO2 suggest that these reactions may facilitate isomerization to 2-hydroperoxypropene, possibly by subsequent reactions of association products.

Simulation of the photodetachment spectrum of HHfO- using coupled-cluster calculations.

The photodetachment spectrum of HHfO- was simulated using restricted-spin coupled-cluster single-double plus perturbative triple {RCCSD(T)} calculations performed on the ground electronic states of HHfO and HHfO-, employing basis sets of up to quintuple-zeta quality. The computed RCCSD(T) electron affinity of 1.67 ± 0.02 eV at the complete basis set limit, including Hf 5s25p6 core correlation and zero-point energy corrections, agrees well with the experimental value of 1.70 ± 0.05 eV from a recent photodetachment study [X. Li et al., J. Chem. Phys. 136, 154306 (2012)]. For the simulation, Franck-Condon factors were computed which included allowances for anharmonicity and Duschinsky rotation. Comparisons between simulated and experimental spectra confirm the assignments of the molecular carrier and electronic states involved but suggest that the experimental vibrational structure has suffered from poor signal-to-noise ratio. An alternative assignment of the vibrational structure to that suggested in the experimental work is presented.

A theoretical study of the atmospherically important radical-radical reaction BrO + HO2; the product channel O2(a1Δg) + HOBr is formed with the highest rate.

A theoretical study has been made of the BrO + HO2 reaction, a radical-radical reaction which contributes to ozone depletion in the atmosphere via production of HOBr. Reaction enthalpies, activation energies and mechanisms have been determined for five reaction channels. Also rate coefficients have been calculated, in the atmospherically important temperature range 200-400 K, for the two channels with the lowest activation energies, both of which produce HOBr: (R1a) HOBr(X1A') + O2(X3Σ) and (R1b) HOBr(X1A') + O2(a1Δg). The other channels considered are: (R2) BrO + HO2 → HBr + O3, (R3) BrO + HO2 → OBrO + OH and (R4) BrO + HO2 → BrOO + OH. For all channels, geometry optimization and frequency calculations were carried out at the M06-2X/AVDZ level, while relative energies of the stationary points on the reaction surface were improved at a higher level (BD(TQ)/CBS or CCSD(T)/CBS). The computed standard reaction enthalpies (ΔH) for channels (R1a), (R1b), (R2), (R3) and (R4) are -47.5, -25.0, -4.3, 14.9 and 5.9 kcal mol-1, and the corresponding computed activation energies (ΔE) are 2.53, -3.07, 11.83, 35.0 and 37.81 kcal mol-1. These values differ significantly from those obtained in earlier work by Kaltsoyannis and Rowley (Phys. Chem. Chem. Phys., 2002, 4, 419-427), particularly for channel (R1b), and reasons for this are discussed. In particular, the importance of obtaining an open-shell singlet wavefunction, rather than a closed-shell singlet wavefunction, for the transition state of this channel is emphasized. Rate coefficient calculations from computed potential energy surfaces were made for BrO + HO2 for the first time. Although channel (R1a) is the most exothermic, channel (R1b) has the lowest barrier height, which is negative (at -3.07 kcal mol-1). Most rate coefficient calculations were therefore made for (R1b). A two transition state model has been used, involving an outer and an inner transition state. The inner transition state was found to be the major bottleneck of the reaction with the outer transition state having essentially no effect on the overall rate coefficient (k) in the temperature range considered. Studying the entropy, enthalpy and free energy of activation of this channel as a function of temperature shows that the main contributor to the magnitude of ln k at a selected temperature is the entropy term (ΔS#/kB) whereas the temperature dependence of ln k is determined mainly by the enthalpy term (-ΔH#/kBT). This compares with reactions with positive barrier heights where the enthalpy term makes a bigger contribution to ln k. Comparison of the computed rate coefficients with available experimental values shows that the computed values have a negative temperature dependence, as observed experimentally, but are too low by approximately an order of magnitude at any selected temperature in the range 200-400 K.

Simulation of the single-vibronic-level emission spectra of HAsO and DAsO.

The single-vibronic-level (SVL) emission spectra of HAsO and DAsO have been simulated by electronic structure/Franck-Condon factor calculations to confirm the spectral molecular carrier and to investigate the electronic states involved. Various multi-reference (MR) methods, namely, NEVPT2 (n-electron valence state second order perturbation theory), RSPT2-F12 (explicitly correlated Rayleigh-Schrodinger second order perturbation theory), and MRCI-F12 (explicitly correlated multi-reference configuration interaction) were employed to compute the geometries and relative electronic energies for the X̃(1)A(') and Ã(1)A(″) states of HAsO. These are the highest level calculations on these states yet reported. The MRCI-F12 method gives computed T0 (adiabatic transition energy including zero-point energy correction) values, which agree well with the available experimental T0 value much better than previously computed values and values computed with other MR methods in this work. In addition, the potential energy surfaces of the X̃(1)A(') and Ã(1)A(″) states of HAsO were computed using the MRCI-F12 method. Franck-Condon factors between the two states, which include anharmonicity and Duschinsky rotation, were then computed and used to simulate the recently reported SVL emission spectra of HAsO and DAsO [R. Grimminger and D. J. Clouthier, J. Chem. Phys. 135, 184308 (2011)]. Our simulated SVL emission spectra confirm the assignments of the molecular carrier, the electronic states involved, and the vibrational structures observed in the SVL emission spectra but suggest a loss of intensity in the reported experimental spectra at the low emission energy region almost certainly due to a loss of responsivity near the cutoff region (∼800 nm) of the detector used. Computed and experimentally derived re (equilibrium) and/or r0 {the (0,0,0) vibrational level} geometries of the two states of HAsO are discussed.

A Study of H2O2 with Threshold Photoelectron Spectroscopy (TPES) and Electronic Structure Calculations: Redetermination of the First Adiabatic Ionization Energy (AIE).

In this work, hydrogen peroxide has been studied with threshold photoelectron (TPE) spectroscopy and photoelectron (PE) spectroscopy. The TPE spectrum has been recorded in the 10.0-21.0 eV ionization energy region, and the PE spectrum has been recorded at 21.22 eV photon energy. Five bands have been observed which have been assigned on the basis of UCCSD(T)-F12/VQZ-F12 and IP-EOM CCSD calculations. Vibrational structure has only been resolved in the TPE spectrum of the first band, associated with the X̃(2)Bg H2O2(+) ← X̃(1)A H2O2 ionization, on its low energy side. This structure is assigned with the help of harmonic Franck-Condon factor calculations that use the UCCSD(T)-F12a/VQZ-F12 computed adiabatic ionization energy (AIE), and UCCSD(T)-F12a/VQZ-F12 computed equilibrium geometric parameters and harmonic vibrational frequencies for the H2O2 X̃(1)A state and the H2O2(+) X̃(2)Bg state. These calculations show that the main vibrational structure on the leading edge of the first TPE band is in the O-O stretching mode (ω3) and the HOOH deformation mode (ω4), and comparison of the simulated spectrum to the experimental spectrum gives the first AIE of H2O2 as (10.685 ± 0.005) eV and ω4 = (850 ± 30) and ω3 = (1340 ± 30) cm(-1) in the X̃(2)Bg state of H2O2(+). Contributions from ionization of vibrationally excited levels in the torsion mode have been identified in the TPE spectrum of the first band and the need for a vibrationally resolved TPE spectrum from vibrationally cooled molecules, as well as higher level Franck-Condon factors than performed in this work, is emphasized.

Can Cyclen Bind Alkali Metal Azides? A DFT Study as a Precursor to Synthesis.

Can cyclen (1,4,7,10-tetraazacyclododecane) bind alkali metal azides? This question is addressed by studying the geometric and electronic structures of the alkali metal azide-cyclen [M(cyclen)N3] complexes using density functional theory (DFT). The effects of adding a second cyclen ring to form the sandwich alkali metal azide-cyclen [M(cyclen)2N3] complexes are also investigated. N3(-) is found to bind to a M(+) (cyclen) template to give both end-on and side-on structures. In the end-on structures, the terminal nitrogen atom of the azide group (N1) bonds to the metal as well as to a hydrogen atom of the cyclen ring through a hydrogen bond in an end-on configuration to the cyclen ring. In the side-on structures, the N3 unit is bonded (in a side-on configuration to the cyclen ring) to the metal through the terminal nitrogen atom of the azide group (N1), and through the other terminal nitrogen atom (N3) of the azide group by a hydrogen bond to a hydrogen atom of the cyclen ring. For all the alkali metals, the N3-side-on structure is lowest in energy. Addition of a second cyclen unit to [M(cyclen)N3] to form the sandwich compounds [M(cyclen)2N3] causes the bond strength between the metal and the N3 unit to decrease. It is hoped that this computational study will be a precursor to the synthesis and experimental study of these new macrocyclic compounds; structural parameters and infrared spectra were computed, which will assist future experimental work.