Density functional theory analysis of CaRgn complexes: (Rg=He, Ne, Ar; n=1–4)

CaRg_n⁺ (Rg=He, Ne, Ar) complexes with n=1–4, are investigated by performing using the B3LYP/6-311+G (3df) density functional theory calculations. The CaHe_n⁺ (n=1–4) complexes are found to be stable. In the case of CaNe_n⁺ and CaAr_n⁺, stable structures and stationary point were found only for n=1 and 2. For n=3 in the C_3V and the D_3h point group as well as for n=4 in the T_d (tetrahedral) point group a saddle point (imaginary frequency) is observed and global minimum could be obtained along the potential energy surface.     

Pathway studies in the fragmentation of Ge(CH3)4 involving Ge(3d,3p,3s) and C(1s) inner-shell photoexcitation in the range 49.5–450 eV

The dissociative multiple photoionization of tetramethylgermane (Ge(CH₃)₄) in the valence, and in the Ge(3d,3p,3s) and C(1s) inner-shell regions has been studied by using time-of-flight mass spectrometry coupled to synchrotron radiation in the range 49.5–450 eV. Total and individual photoion yields have been recorded as a function of the incident photon energy. Several discrete resonances over a structureless giant resonance are observed below the Ge(3p), Ge(3s) and C(1s) threshold regions. The structureless giant resonance corresponding to the Ge(3d) presumably arises from the continuum enhancement caused by the 3d→εf transition. Various monocations of H⁺, H₂⁺, CH_n⁺ (n=0–4), C₂H_n⁺ (n=0–5), GeH_n⁺, GeCH_n⁺, GeC₂H_n⁺, and GeC₃H_n⁺ are detected in the whole energy range. Dissociation processes have also been investigated by photoelectron–photoion and photoion–photoion coincidence methods. The dominant dissociation channel is found to be CH_n⁺–GeCH_n⁺ in the whole energy examined. Specific energy dependence of dissociation processes is observed in the Ge(3p) and Ge(3s) regions. With the help of ab initio HF/6-311++G(2df,p) calculation, we roughly estimated the photoabsorption positions and symmetries for the discrete core hole states.     

Theoretical study on the structure and stability of hydrogen-ion clusters Hn and Hn (n = 3, 5, 7, 9, 11, 13)

Ab initio SCF and CI calculations have been carried out for H_n⁺ and H_n⁻ (n = 3, 5, 7, 9, 11, 13) clusters with a double-zeta plus polarization basis set. The stabilization energy of negative ion clusters H_n⁻ is very small (less than 1 kcal) and their existence is critical. The structural difference between positive- and negative-ion clusters are discussed in terms of the bonding ability involved. While H_n⁺ is a charge-transfer complex, the stability of H_n⁻ comes mainly from the ion-induced-dipole attractions. The electron correlation effect on the structure and stability of these ion clusters is also discussed.     

First principles study of the structure, electronic state and stability of SinCm anions

Structure, electronic state and energy of Si_nC⁻ and Si_nC⁻₂ (n=1–7) anions have been investigated using the density functional theory. Structural optimization and frequency analysis are performed at the level B3LYP/6-311G(d). The charged-induced structural changes in these anions have been discussed. The strong C–C bond is also favored over C–Si bonds in the Si_nC⁻_m anions in comparison with corresponding neutral cluster. Among different Si_nC⁻ and Si_nC⁻₂ (n=1–7) anions, Si₃C⁻, Si₅C⁻ and Si₂C⁻₂ are most stable. Their stability has a decreasing tendency with the increase in the size of these clusters.     

A Fourier-transform ion-cyclotron-resonance study of the reactions of polycyclic aromatic hydrocarbon cations with molecules of interstellar interest

The reactivity of naphthalene and pyrene radical cations and their derivatives (C₁₀H_n⁺, n=6,7,8,9), C₁₆H_n (n=9,10,11) has been studied with molecules of interstellar interest in an ion cyclotron resonance apparatus. The radical cations C₁₀H₈⁺ and C₁₆H₁₀⁺ are unreactive with H₂,CO,H₂O and NH₃. Adduct formation is the only channel for almost all reactions of C₁₀H₇⁺ with these molecules. The implications of these results for the stability of polycyclic aromatic hydrocarbon (PAH) cations in the interstellar medium are briefly discussed. Exploratory studies of the ion chemistry of a larger PAH, coronene, have also been done.     

Complexes of cationic coinage metal clusters Mn (M=Cu, Ag, Au; n=1–4) and H2S: a theoretical study

Geometries and vibrational frequencies of complexes of cationic coinage metal clusters M_n⁺ (M=Cu, Ag, Au; n=1–4) and H₂S are computed using density functional theory. Thermochemical values for M_n⁺H₂S decomposition channels involving loss of an H atom, H₂ molecule, M atom, or M₂ molecule are also computed. Significantly different results are obtained for closed-shell (n odd) and open-shell (n even) complexes.     

Ab initio MRD-CI study of GaAs, GaAs2(±), Ga2As2(±) and As4 clusters

Using pseudopotentials and double zeta basis sets with s, p diffuse functions and two sets of d functions, MRD-CI calculations were performed on As₂^(±), As₄⁽⁺⁾, GaAs⁻, GaAs₂^(±) and Ga₂As₂^(±). This study complements previous theoretical investigations on Ga^(±) to Ga₄^(±) and GaAs⁽⁺⁾. For As₄ tetrahedral symmetry was assumed, and Re of X¹A₁ determined as 4.73a₀. Vertical ionization potentials to several states of As₄⁺ were calculated. For GaAs₂, GaAs₂⁺ and GaAs₂⁻, ground and one low-lying state were geometry-optimized, both in C_2v (Ga-As-As), and linear symmetry (GaAsAs, C_∞h and AsGaAs, D_∞h). The lowest state of GaAs₂ is ²B₂ in C_2v. For Ga₂As₂, the lowest state and low-lying excited states were optimized in various geometries. The most stable state has rhombic structure (¹A_g in D_2h), but T-form and other forms (C_2v, C_∞v, D_∞h) are only 1–2 eV less stable. In D_2h symmetry, several low-lying excited states of Ga₂As₂ were studied. The ground states of Ga₂As₂⁺ and Ga₂As₂⁻ were found to be ²B_2u, and ²B_2g, respectively. Trends in ionization potentials (IP), electron affinities (EA), atomization energies and fragmentation energies for the molecules Ga_xAs_y and the pure compounds Ga_n and As_n up to 4 atoms, were studied. Ga_xAs_y clusters, with x + y even, have higher IP's than odd-numbered clusters. An experimentally observed alternation of EA, whereby an odd number of atoms have higher EA than their even neighbors, is confirmed. The mixed compounds Ga_xAs_y have atomization energies between those of Ga_n and As_n (x + y = n), usually closer to those of Ga_n. Fragmentation of Ga_xAs_y occurs such that As----As bonds are retained, and if possible, also Ga----As bonds, since the dissociation energy of As₂ is higher than that of GaAs, which in turn is higher than that of Ga₂. Calculated fragmentation energies agree qualitatively with experimental observations about the composition of 3-atomic and 4-atomic clusters Ga_xAs_y.     

Binding energies and electronic structures of Cu(OH2)n and Cu(NH3)n (n=1–4): anomaly of the two ligand Cu complexes

Ab initio calculations up to MP4(SDTQ) level and density functional theory have been used to estimate binding energies and electronic structures of Cu⁺(L)_n (L=OH₂, NH₃, n=1–4) complexes using TZP basis set types. The computed binding energies agree well with experimental values. General trends in structures and energetics are recorded for both Cu⁺(OH₂)_n and Cu⁺(NH₃)_n systems. The first two ligands are more strongly bound to Cu⁺ than the third and fourth molecules. The 4s–3dσ hybridization and electrostatic interactions are the main factors behind the higher binding energies for the first two ligands. Analysis of HOMO mixed orbitals in the copper ion as well as in complexes indicates shrinking of the orbital lobes directed to the ligand with shrinking more effective in the two ligand system. The lower binding energies for the third and fourth ligands were attributed to the attenuation of sdσ hybridization and decreasing of Cu–L attraction at long separation which is necessary to relieve Cu–L and L–L exchange repulsions. NBO analysis and charge-model calculations support the presence of sdσ hybridization and electron transfer to the copper ion in case of the first two ligands.     

Simultaneous determination of anions and cations by ion-exclusion chromatography–cation-exchange chromatography with tartaric acid/18-crown-6 as eluent

Ion-exclusion chromatography–cation-exchange chromatography was developed for the simultaneous separation of common inorganic anions and cations (Cl⁻, NO₃⁻ and SO₄²⁻; Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺) on a weakly acidic cation-exchange column by elution with weak acid. Generally, the resolution among these monovalent cations was only moderate, thereby hindering the determination of these analytes in natural-water samples. Therefore, 18-crown-6 was added to the eluent to improve the resolution. A good separation of these anions and cations on a weakly acidic cation-exchange column was achieved in 30 min by elution with 5 mM tartaric acid/6 mM 18-crown-6/methanol–water (7.5:92.5). The ion-exclusion chromatography–cation-exchange chromatography method developed here was successfully applied to the separation of major anions and cations in an environmental water sample.     

Preparation, properties, and reactions of metal-containing heterocycles: Part CV. Synthesis and structure of polyoxadiphosphaplatinaferrocenophanes

A series of novel heterobimetallic crown ether-like polyoxadiphosphaplatinaferrocenophanes cis-[1,1′-Fc(CH₂O(CH₂CH₂O)_nCH₂CH₂PPh₂)₂]PtCl₂ (n=1–3) (4a–c) was synthesized in good yield by cyclization of the bis(phosphine) ligands 1,1′-Fc(CH₂O(CH₂CH₂O)_nCH₂CH₂PPh₂)₂ (n=1–3) (3a–c) and (PhCN)₂PtCl₂ under high dilution conditions in CH₂Cl₂. The bisphosphines 3a–c are obtained by reaction of the corresponding diols 1,1′-Fc(CH₂O(CH₂CH₂O)_nCH₂CH₂OH)₂ (n=1–3) (1a–c) with: (i) CH₃SO₂Cl in CH₂Cl₂ and (ii) LiPPh₂ in THF. Although the X-ray crystal structure of 4a shows that the cavity is large enough for the encapsulation of small metal cations, inclusion experiments of 4a–c with Group 1 cations, and Mg²⁺, or NH₄⁺ in solution applying NMR titration and cyclovoltammetric methods reveal no evidence for the formation of host–guest complexes for 4a,b. In the case of 4c only the addition of Na⁺ or K⁺ leads to an insignificant effect.     

Ionization of NF3 by electron impact

The ionization and dissociative ionization of NF₃ by electron impact has been measured by Fourier transform mass spectrometry (FTMS). The total ionization cross-section rises to a maximum value of 2.4±0.4×10⁻¹⁶ cm² at 140 eV. Estimates of the total single ionization cross-section using ab initio energies with the binary encounter Bethe (BEB) [Y.K. Kim, M.E. Rudd, Phys. Rev. A 50 (1994) 3594] or Deutsch–Märk [Int. J. Mass Spec. 197 (2000) 37] models are roughly twice the measured values. The partial cross-sections creating NF_x⁺ (x=0, 1, 2, 3), F⁺, and NF_x²⁺ (x=1, 2, 3) are reported. Differences between the FTMS results and quadrupole data and fast atom beam results of Tarnovsky et al. [Int. J. Mass Spectrom. Ion Processes 133 (1994) 175] are discussed.     

Ligand deprotonation significance in the formation of the molybdate ion-malic acid complexes

Using the temperature jump technique, the study of the kinetics of the complexing of oxomolybdate anion with malic acid has been carried out in aqueous solutions of pH 7.15–8.5 at ionic strength 0.1 M (KNO₃) and 25°'C. A reaction scheme for the formation of 1 : 1 complexes is proposed which accounts for the observed relaxation rates.

The significance of the ligand deprotonation on the complexation reaction of MoO₄²⁻ by a single protonated ligand, i.e. MoO₄²⁻+LH^nk→MoO₃(OH)Lⁿ⁻², (where n = 1 -, 2 -, etc), is analysed on the basis of a simple model. A linear correlation between the log k and the pK of the monoprotonated ligand (LH) is found for this reaction when the global process is controlled by the proton transfer from the ligand to an oxogroup, i.e. log k = a - 0.5xpK. It is found that this correlation is satisfied by MoO₄²⁻ and WO₄²⁻. The experimental slopes for these oxyanions are −0.503 and −0.543 respectively, in agreement with the predictions.     

Thermochemical properties of molecules and cations of MgNnHm (n=1,2 and m=1–6): enthalpies of formation, proton affinities and ionization energies

Ab initio molecular orbital calculations are reported for small neutral molecules and cations containing magnesium, nitrogen and hydrogen. Structures have been optimized using gradient techniques at B3LYP/6-31+G(d) and at MP2(full)/6-311++G(d,p). Single-point calculations are reported at QCISD(T)(full)/6-311++G(2df,p) and at CCSD(T)(full)/6-311++G(2df,p) levels using geometries optimized at MP2(full)/6-311++G(d,p). Standard enthalpies of formation at 298 K have been calculated at these two higher levels of theory. Other thermochemical properties calculated include ionization energies and proton affinities. The binding enthalpies of ammonia to Mg⁺, MgNH₂⁺ and MgNH₃⁺ are also reported.     

Structures and energetics of C3H6S isomers: a Gaussian-3 ab initio study

Twenty-two isomers/conformers of C₃H₆S^+√ radical cations have been identified and their heats of formation (ΔH_f) at 0 and 298 K have been calculated using the Gaussian-3 (G3) method. Seven of these isomers are known and their ΔH_f data are available in the literature for comparison. The least energy isomer is found to be the thioacetone radical cation (4⁺) with C_2v symmetry. In contrast, the least energy C₃H₆O^+√ isomer is the 1-propen-2-ol radical cation. The G3 ΔH_f298 of 4⁺ is calculated to be 859.4 kJ mol⁻¹, ca. 38 kJ mol⁻¹ higher than the literature value, ≤821 kJ mol⁻¹. For allyl mercaptan radical cation (7⁺), the G3 ΔH_f298 is calculated to be 927.8 kJ mol⁻¹, also not in good agreement with the experimental estimate, 956 kJ mol⁻¹. Upon examining the experimental data and carrying out further calculations, it is shown that the G3 ΔH_f298 values for 4⁺ and 7⁺ should be more reliable than the compiled values. For the five remaining cations with available experimental thermal data, the agreement between the experimental and G3 results ranges from fair to excellent.

Cation CH₃CHSCH₂^+√ (10⁺) has the least energy among the eleven distonic radical cations identified. Their ΔH_f298 values range from 918 to 1151 kJ mol⁻¹. Nevertheless, only one of them, CH₂=SCH₂CH₂^+√ (12⁺), has been observed. Its G3 ΔH_f298 value is 980.9 kJ mol⁻¹, in fair agreement with the experimental result, 990 kJ mol⁻¹.

A couple of reactions involving C₃H₆S^+√ isomers CH₂=SCH₂CH₂^+√ (12⁺) and trimethylene sulfide radical cation (13⁺) have also been studied with the G3 method and the results are consistent with experimental findings.     

Mercury(II) halide adducts of an olefinic double betaine: [{Hg2L2X4·6HgX2}n] [X = Cl, Br; L = cis-(p-Me2NC5H4N)2C2(COO)2]

Two polymeric mercury(II) halide adducts of an olefinic double betaine, cis-(p-Me₂NC₅H₄N⁺)₂C₂(COO⁻)₂ (L), have been prepared and characterized by X-ray crystallography. [{Hg₂L₂Cl₄·6HgCl₂}_n] (1) crystallizes in the monoclinic space group C2/c with Z = 4, and [{Hg₂L₂Br₄·HgBr₂}_n] (2) in the triclinic space group P with Z = 1. Complexes 1 and 2 are structurally similar, being composed of centrosymmetric fourteen-membered rings and nearly linear HgX₂ (X = Cl, Br) moieties that are further inter-linked by weak HgX [HgCl = 2.930–3.136(9) Å, HgBr = 3.057–3.310(6) Å] and HgO [2.64, 2.75(3) Å] bonds to generate a two-dimensional polymeric network.     

Density functional and multiphoton ionization studies of N,N-dimethylformamide–(methanol)n clusters

The multiphoton ionization of the hydrogen-bonded clusters N,N-dimethylformamide–(methanol)_n (DMF–(CH₃OH)_n) was studied using a time-of-flight mass spectrometer at the wavelengths of 355 and 532 nm. At both wavelengths, a series of protonated DMF–(CH₃OH)_nH⁺ ions was obtained. The clusters were also investigated by density functional theory B3LYP method in conjunction with basis sets 6-31+G(d,p) and 6-311+G(2d,p). Equilibrium geometries of both neutral and ionic DMF–CH₃OH clusters, and dissociation channels and dissociation energies of the ionic clusters are presented. The results show that when DMF–CH₃OH is vertically ionized and dissociated, DMFH⁺ and CH₃O are the dominant products via proton transfer reaction. A high energy barrier makes another channel corresponding to the production of DMFH⁺ and CH₂OH disfavored. In the DMF–(CH₃OH)H⁺ ion, the proton prefers to link with the O atom of DMF molecule. Variation of atomic charges during proton transfer in hydrogen bond of the protonated cluster DMF–(CH₃OH)H⁺ ion is also discussed.     

第一性原理研究混合钙钛矿CH3NH3PbxSn1－xI3结构及光电特性

有机/无机钙钛矿是一类极具潜质的光电材料,目前已实现超过20%的光电转化效率。本文采用第一性原理对有机/无机混合钙钛矿CH₃NH₃Pb_xSn_1-xI₃ (x = 0-1)的结构及光电特性进行了理论研究。结果表明,范德华力(VDW)在优化钙钛矿结构中起着重要的作用,考虑范德华力可减小Pb/Sn―I键长,从而减小体系体积。通过分析甲胺离子CH₃NH₃⁺的态密度和Bader电荷,我们发现其对前线轨道没有贡献,仅仅扮演电荷供体的角色。Pb/Sn与I之间同时存在共价键和离子键相互作用。价带顶(VBM)主要是由I 5p以及Pb 6s (Sn 5s)杂化组成,而导带底(CBM)主要由Pb 6p (Sn 5p)轨道组成。在可见光区,随着波长的增加,体系吸收强度呈现整体下降趋势;随着Sn/Pb比值逐渐增大,吸收强度呈现增大趋势。CH₃NH₃SnI₃在可见光区表现出较佳的吸收光谱特性。     

A theoretical study of protonated OCnOH ions, n=3–8

Since ion-neutral reactions are a major component of the processes driving interstellar chemistry, most reaction network include protonated species. Besides, these ions are able to initiate chemical processes that would not occur with their neutral parents. In this contribution we report a systematic study of the protonated adducts of the OC_nO series (n=3–8) using the B3LYP level of theory. The structures of all possible O-protonated and C-protonated isomers of [OC_nOH⁺] have been determined together with their rotational constants, vibrational frequencies and intensities. Although it appears that these ions belong to two different series, odd-n and even-n, it is found that protonation occurs at the carbons second to the terminal oxygens for all n. The most stable structure is found to be the singlet ion whatever the singlet or triplet spin state of the parent species. However, due to the lack of efficient spin–orbit coupling, only the odd series [OC_nOH⁺] with n=3,5,7 should be formed on the singlet ground state surface. Analysis of the infrared intensities shows that the spectra are dominated by only one or two very strong bands (CC stretching) that carry most of the overall intensity in the 2200–2350 cm⁻¹ region.     

Vibrational dependence of the NH3 (v2)+NO and NO(v)+NH3 charge transfer cross sections

A tandem quadrupole mass spectrometer is used to study the charge transfer reactions NH₃⁺ + NO and NO⁺ + NH₃ over a collision energy range 1.5–13 eV. The vibrational state of the reagent ions is selected by resonance-enhanced multiphoton ionization. For the 0.9 eV exothermic process NH₃⁺ + NO → NH₃ + NO⁺ excitation of the v₂ umbrella bending mode (v₂ = 0–12) causes no marked change in the charge transfer cross section, while in the reverse process NO⁺ + NH₃ → NO + NH₃⁺ excitation of the NO⁺ vibration (v = 0–6) strongly enhanced the charge transfer cross section.     

Coordination geometry of chromium(VI) species. The first example of cis-bridging chromate ions in helically structured catena(μ-CrO4-O,O′)[Ni(HIm)3H2O]

Nickel(II) chromate complex with imidazole (HIm) was isolated from the [Ni²⁺–HIm–CrO₄²⁻] system in various experimental conditions, i.e. reagent molar ratios and nickel(II) salts. The catena(μ-CrO₄-O,O′)[Ni(HIm)₃H₂O] (1) crystallizes in monoclinic crystal system—space group P2₁/n with cell parameters: a=11.784(2), b=8.899(2), c=13.934(3) (Å), β=95.19(3) (°). The unit cell contains two independent helixes, left- and right-handed, stabilized by intrahelical and interhelical hydrogen bonds (HB) and π–π interactions. The cis coordination of the CrO₄²⁻ anions and the HB systems appeared to be the main determinants of the helical architecture. To the best of our knowledge the cis-chromate coordination was observed for the first time. The cis coordination causes the distortion of the nickel octahedron, which was analysed by 4 K single crystal electronic spectra with D_4h symmetry approximation (gaussian resolution and crystal field parameters). This symmetry was also confirmed with the polarised electronic spectra. The magnetic properties of the complex suggest the occurrence of weak intrachain antiferromagnetic interactions between the magnetic Ni^II center. The computational DFT studies of complex 1 assuming three possible isomers mer[(HIm)₃]–cis[(CrO₄²⁻)₂], mer–trans and fac–cis suggested that the main contribution to the stability of 1 might have interhelical and intrahelical hydrogen bonds.