The reactions of Cl+ (3P) and Cl+ (1D) with hydrogen sulphide. A G2 molecular orbital study

G2 ab initio molecular orbital calculations have been performed to study the potential energy surfaces (PESs) associated with the reactions of Cl⁺ in its ³P ground state and in its ¹D first excited state with hydrogen sulphide. [H₂, Cl, S]⁺ singlet and triplet state cations present very different bonding characteristics. The latter are systematically ion-dipole or hydrogen-bonded weakly bound species, while the former are covalent molecular ions. As a consequence, although the Cl⁺(³P) is 34.5 kcal mol^?1 more stable than Cl⁺(¹D), the global minimum of the singlet PES lies 37.3 kcal mol^?1 below the global minimum of the triplet PES. Both singlet and triplet potential energy surfaces show significant differences with respect to those associated with Cl⁺ + H₂O reactions as well as with SH₂ reactions with F⁺. In both cases, the major product should be SH⁺ ₂; SH⁺ and HCl⁺ being the minor products, in agreement with the experimental evidence. The estimated heat of formation for the most stable H₂SCl⁺ singlet state species is 198 ± 1 kcal mol^?1.     

Thermochemistry of the reactions between CN+ and H2O in the gas phase

The [H₂, C, N, 0]⁺ potential energy surface (PES) has been explored by means of high-level ab initio calculations, carried out in the framework of the G2 theory. From this survey we concluded that the predominant products of the CN⁺ + H₂O reaction are the result of the dissociation of HNCOH⁺ species and to a much lesser extent of the CNHOH⁺ cation to yield CNH⁺ + OH. According to our results HCN⁺ should not be a product of this reaction because all pathways leading to its formation are unfavourable with regards to other competitive processes. Other reactive channels lead to the formation of the H₂ONC⁺ structure which dissociates into CN + H₂O⁺. The loss of NH(3σ) and O(³P) seems to take place following spin-forbidden reaction paths through an intersystem crossing between the singlet and the triplet PESs. The global minimum of the PES, H₂NCO⁺ is easily accessible and should lead to the loss of carbon monoxide which has not been experimentally observed in CN⁺ + H₂O reactions. We cannot offer a clear explanation for this disagreement between theory and experiment.     

Spin populations and free valences in excited molecules and in radicals

Using the DFT PBE0 quantum-chemical method, we have determined the spin populations and the free valences of atoms in (i) 3,4-dimethylenefuran; (ii) exciplex 3,4-dimethylenefuran · O₂; (iii) phthalocyaninates PcCu and PcCo; (iv) cations Pc⁺Cu, Pc⁺Co, and Pc⁺Ni; (v) dication [PcAlOAlPc]²⁺; and (vi) two excited triplet diketones: fulleroid-type C₅₈(CO)₂ and cyclododeca-3,4,9,10-tetraene-1,7-dione. Free valences determine atomic contributions to the doubled variance of the many-electron spin. Unlike spin populations, they are insensitive to the choice of the component of a quasi-degenerate spin state of a chemical compound and account for the regioselectivity of the radical addition to 3,4-dimethylenefuran and the photochemical stability of Pc-containing nanosystems. In a triplet state of C¹²H₁₂O₂, the spin density and the free valence are localized on a single carbonyl group, whereas, in a triplet state of C₅₈(CO)₂, they are delocalized.     

Experimental and theoretical study of dicyanocarbene C(CN)2

Dicyanocarbene C(CN)₂ and its radical cation (m/z 64) were generated by dissociative ionization of tetracyanoethene, dicyanofuroxan and dicyanofurazan and characterized by collisional activation (CA) and neutralization-reionization (NR) mass spectrometries and tandem MS³ experiments performed in a ‘hybrid’ tandem mass spectrometer having a sector-quadrupole-sector configuration. In both neutral and ionized forms, dicyanocarbene is found to be a stable and detectable species. Existence of the peaks at m/z 52, 24 and 12 in the CA/NR spectra suggests however some possible post-collisional rearrangements. The carbene was further studied by ab initio calculations using B3LYP/6-311+G(3df) for geometries and CASPT2(14,12) and MR-SDCI with the cc-pVTZ and aug-cc-pVTZ basis sets for relative energies. The dicyano form NC-C-CN is consistently more stable than its isocyano isomers CN-C-CN and CN-C-NC, irrespective of the electronic state. Each neutral carbene exhibits a triplet ground state lying up to 2.6 eV below the singlets. All the triplet, singlet and ionized states of dicyanocarbene have a linear shape. The other states have either linear or bent shape but small barriers to linearity. Adiabatic ionization energies (IE_a) were estimated as follows: NC-C-CN: 11.3 eV with linear ²Π_u cation; NC-C-NC: 10.4 eV with linear ²Π cation, and CN-C-NC: 9.9 eV with bent ²A₁ cation.     

Wavepacket dynamics and quantum mechanical energy densities in the quartet N+ 2 + O2 system

Surface crossing of the potential energy surfaces (PESs) and the formulation of differentiable PES functions are discussed in the quartet N⁺ ₂ + O₂ system containing the T shape intermediate complex. Consideration of the ion-dipole interaction between N₂ and O₂ fragments due to the induced dipole moment of the neutral molecule gives a good image of the surface crossing between the quartet reactant state (N⁺ ₂ ···O₂) and the quartet product state (N₂ ···O⁺ ₂) for the charge transfer (CT) reaction in terms of the conventional harpooning mechanism. Differentiable functions of PESs are constructed for the reactant and product states that may be applied for 3-dimensional dynamics calculations by means of wavepackets, and examples of 2-dimensional wavepacket dynamics calculations are introduced. Further, electron transfer processes and local electronic nature in the CT reaction are discussed in terms of the quantum mechanical energy densities based on regional density functional theory. Regional partitioning by using the kinetic energy density provides a new concept of electron transfer, and the tension density provides new images of microscopic electronic stresses.     

Theoretical study of charge-exchange and excitation processes in collisions of He<Superscript>+</Superscript> ions with C<Superscript>5+</Superscript>, N<Superscript>6+</Superscript>, and O<Superscript>7+</Superscript> hydrogen-like ions

Data on the cross sections for single-electron charge exchange and excitation in collisions of He⁺ ions with C⁵⁺, N⁶⁺, and O⁷⁺ ions in the He⁺ ion energy range of 0.2–3.0 MeV are obtained for the first time. The cross sections for the single-electron charge transfer into the singlet and triplet 1snl states of C⁴⁺, N⁵⁺, and O⁶⁺ (2≤n≤5) ions and for the 1s → 2p _{0, ±1} electronic excitation of He⁺(1s) ions are calculated. The calculations were performed by solving close-coupling equations on the basis of ten two-electron quasi-molecular states.     

Quantum mechanical studies on the singlet and triplet potential energy surface of the reactions CF3O2 + I,CF3O + OI and CF3 + OIO

The singlet and triplet potential energy surfaces for the reactions CF₃O₂ + I (1), CF₃O + OI (2) and CF₃ + OIO (3) are investigated using ab initio quantum mechanical methods. Four important isomeric energy minima were found, three on the singlet surface, CF₃OOI, CF₃OIO and CF₃IO₂ and one on the triplet surface ³CF₃OIO. CF₂O + FOI are shown to be the most probable products for all reactions, CF₃O +I and CF₃O + O(³P) are possible for reactions (2) and (3) while the reaction pathway leading to CF₃O +OI is also possible for reaction (3).     

Involvement of triplet state in the photodissociation of hydrogen peroxide: experimental evidence from time-resolved EPR study

The dissociation of photoexcited hydrogen peroxide to generate a pair of hydroxyl radicals is generally believed to take place in a repulsive electronic singlet state. The results presented here, based on time-resolved EPR experiments on the spin polarisation pattern of the acetone ketyl radical (CH₃)₂C^?OH, generated on photodissociation of H₂O₂ in 2-propanol with a 248?nm laser light, strongly indicate significant involvement of a repulsive triplet state of excited hydrogen peroxide.     

异戊二烯解离光电离理论研究

利用CBS-QB3理论计算方法研究了异戊二烯的可能解离通道.获得了主要碎片离子C₅H₇⁺,C₅H₅⁺,C₄H₅⁺,C₃H₆⁺,C₃H₅⁺,C₃H₄⁺,C₃H₃⁺的C₂H₃⁺的结构以及这些解离通道的解离能,并给出了相应的过渡态和中间体的结构和位垒.得到的异戊二烯电离势及主要碎片离子的出现势均与实验值符合的较好.最后,通过理论和实验结果的对比讨论了各通道的解离机理.     

Formation of ultracold RbCs molecules by photoassociation

The formation of ultracold metastable RbCs molecules is observed in a double species magneto-optical trap through photoassociation below the ⁸⁵Rb(5S_1/2) + ¹³³Cs(6P_3/2) dissociation limit followed by spontaneous emission. The molecules are detected by resonance enhanced two-photon ionization. Using accurate quantum chemistry calculations of the potential energy curves and transition dipole moment, we interpret the observed photoassociation process as occurring at short internuclear distance, in contrast with most previous cold atom photoassociation studies. The vibrational levels excited by photoassociation belong to the 5th 0⁺ or the 4th 0^? electronic states correlated to the Rb(5P_{1/2, 3/2}) + Cs(6S_1/2) dissociation limit. The computed vibrational distribution of the produced molecules shows that they are stabilized in deeply bound vibrational states of the lowest triplet state. We also predict that a noticeable fraction of molecules is produced in the lowest level of the electronic ground state.     

Doublet and quartet states of Li 2 −

Electronic states of the molecular lithium anion are investigated by configuration-interaction calculations. Comparison with the analogously computed potential energy curves for the lowest singlet and triplet states of the neutral Li₂ shows that in addition to the well-known stable ground state X there also exist metastable excited states of Li ₂ ^- . Within the quartet sector, two candidates for such long-lived states are identified and their spectroscopic properties studied. Received 23 March 1999     

On the bound states in the muonic molecular ions

Absolute cross sections for electron impact ionization and dissociation of OH⁺ and OD⁺ leading to the formation of the OH²⁺, O⁺, O²⁺, O³⁺ and D⁺ ions have been measured by applying the animated electron-ion beam method in the energy range from the respective reaction thresholds up to 2.5 keV. The maximum of the single ionization cross section is found to be (0.95? ± ?0.02) × 10^?19 cm² at 155 eV. The maximum total cross sections for O⁺ and D⁺ fragments production are observed to be (15.7? ± ?0.2) × 10^?17 cm² at 95 eV and (10.8? ± ?0.5) × 10^?17 cm² at 95 eV, respectively. The cross sections for O²⁺ and O³⁺ are much smaller, (5.37? ± ?0.04) × 10^-18 cm² at 135 eV and (7.95? ± ? 0.23) × 10^-20 cm² at 315 eV, respectively. The collected data are analyzed in details in order to determine separately the contributions of dissociative excitation and of dissociative ionization to the O⁺ and D⁺ fragments production.     

Theoretical study of the HeN2+ 2 dication

The structure and stability of the helio nitrogen molecular dication, HeN²⁺ ₂, is investigated by means of standard quantum chemical methods based on both single-reference and multi-reference formalisms. Sequences of correlation consistent basis sets are employed to establish convergence with respect to the size and the quality of the single-particle basis set. MRCI and CASPT2 calculations are reported for the HeN²⁺ ₂ ground-state ion which is found to be metastable. The barrier for the transition state of the reaction HeN²⁺ ₂→ N⁺ …NHe⁺ → N⁺ + NHe⁺ is calculated to be 59.5 kcals mol^?1. The structure of the transition state NHeN²⁺ was also determined from calculations using the MRCI and CASPT2 methods.     

Field ionization of ozone

Experimental results on the field ionization of ozone at an iridium surface using a magnetic sector atom-probe FIM show that at the lowest field of ~1.5 V/Å only 25% of all ions produced are O⁺₃, while O⁺₂ and a small percentage of O⁺ indicate field induced dissociation of ozone and recombination of atomic oxygen into O₂. At high fields and free space ionization, O⁺₂ is predominant, while the atomic oxygen as a dissociation product escapes without being ionized and cannot be detected. Using pure oxygen as an imaging gas in the FIM, O⁺₂ ions do not dissociate under the same conditions.     

Singlet-triplet excitation ratios in Ne III, Ar III and N II under ion impact

Peculiar properties of ion-atom collision systems, in particular deviations from statistical populations of singlet and triplet levels, can be studied by optical spectroscopy. We have extended earlier studies by VUV spectroscopy of a number of collision systems at various collision energies in the 0.01-MeV/nucleon to 1-MeV/nucleon range, involving H₂ ⁺, H⁺, He⁺, He²⁺, Ne⁺, Ar⁺, and N₂ ⁺ as projectiles and Ne, Ar, and N₂ as target gases. Statistically significant deviations of the relative intensities of singlet and triplet lines from simple ratios are observed in the displaced terms of the valence shell of Ne III, corroborating and extending earlier work. For Ar III, the energy dependences of singlet-to-triplet excitation ratios are very different for different projectiles. For N II, in contrast, all observed line ratios are practically independent of the projectile energy. Received 17 November 2000 and Received in final form 31 January 2001     

甲烷分子电子碰撞电离和解离的实验研究

本文利用反应显微成像技术(reaction microscope)研究了54 eV电子入射甲烷分子导致的电离解离过程,详细分析了电离解离产生的CH⁺₂,CH⁺,C⁺离子碎片的动能分布情况.实验结果表明,该入射能量下产生CH⁺₂,CH⁺,C⁺离子碎片主要贡献来自2a₁内价轨道电子的直接电离过程产生的离子态(2a< 关键词： 反应显微成像谱仪 电离解离 能量沉积 动能分布     

Relaxing Phenomena in Negative Corona Discharge: New Aspects

Two theories, explaining the time dependence of the negative corona discharge current in air, are confronted with new experimental results. The influence of the ozone concentration on the discharge current was experimentally confirmed in dry air and in mixtures of nitrogen with oxygen. Assuming that only the dissociative electron attachment to ozone molecule is a process being responsible for a reduction of the electron component in the total mean discharge current, the mean value of the electron attachment rate constant k = (3 - 5.5) × 10^?9 cm^?3 s^?1 was derived from the measured dependence of the discharge current on the ozone concentration. The calculated value of the rate constant k corresponds to the dissociative attachment of electron to ozone molecule via process e + O₃ → products (O^? or O^?₂ negative ions).     

Pentacene Nanorods as Effective Photosensitizer for Photodynamic Therapy of Tumor via Singlet Fission

Singlet fission (SF), whereby a singlet exciton is converted into a pair of triplet excitons, can improve the efficiency of solar cells. Pentacene has been extensively studied as the most promising SF compound, owing to its 200% yield of triplet states. However, the easy degradation of pentacene in the presence of light and air owing to photooxidation cannot be explained by the classical ¹O₂ generation mechanism. To address this issue, in the present study, pentacene nanorods (Pc NRs) are prepared as a novel photosensitizer (PS); self-carried Pc NRs exhibited higher ¹O₂ generation capacity. Thus, a novel ¹O₂ generation mechanism is proposed based on the SF effect. The initial photon absorption occurs to access single-exciton states, S1–S3. Excited-state Pc pairs accelerate the SF effect in pentacene NRs, leading to a non-adiabatic transition to the dark D state. Dark D state is a singlet state by two triplets coupled overall, and it can transfer its energy to ³O₂ for generating ¹O₂. Using Pc NRs as PSs, photodynamic therapy (PDT) inhibits tumor growth in 4T1 tumor-bearing mice upon 405-nm-wavelength and 650-nm-wavelength laser irradiations. This study paves the way to discover novel PSs that are not considered with classical ¹O₂ generation mechanisms.     

Surface-induced magnetism of the solids with impurities and vacancies

Using the quantum-mechanical approach combined with the image charge method we calculated the lowest energy levels of the impurities and neutral vacancies with two electrons or holes located in the vicinity of flat surface of different solids. Unexpectedly we obtained that the magnetic triplet state is the ground state of the impurities and neutral vacancies in the vicinity of surface, while the nonmagnetic singlet is the ground state in the bulk, for e.g. He atom, Li⁺, Be⁺⁺ ions, etc. The energy difference between the lowest triplet and singlet states strongly depends on the electron (hole) effective mass μ, dielectric permittivity of the solid ε₂ and the distance from the surface z₀. For z₀=0 and defect charge ∣Z∣=2 the energy difference is more than several hundreds of Kelvins at μ=(0.5−1)m_e and ε₂=2-10, more than several tens of Kelvins at μ=(0.1−0.2)m_e and ε₂=5-10, and not more than several Kelvins at μ<0.1m_e and ε₂>15 (m_e is the mass of a free electron). Pair interaction of the identical surface defects (two doubly charged impurities or vacancies with two electrons or holes) reveals the ferromagnetic spin state with the maximal exchange energy at the definite distance between the defects (∼5-25 nm). We estimated the critical concentration of surface defects and transition temperature of ferromagnetic long-range order appearance in the framework of percolation and mean field theories, and RKKY approach for semiconductors like ZnO. We obtained that the nonmagnetic singlet state is the lowest one for a molecule with two electrons formed by a pair of identical surface impurities (like surface hydrogen), while its next state with deep enough negative energy minimum is the magnetic triplet. The metastable magnetic triplet state appeared for such molecule at the surface indicates the possibility of metastable ortho-states of the hydrogen-like molecules, while they are absent in the bulk of material. The two series of spectral lines are expected due to the coexistence of ortho- and para-states of the molecules at the surface. We hope that obtained results could provide an alternative mechanism of the room temperature ferromagnetism observed in TiO₂, HfO₂, and In₂O₃ thin films with contribution of the oxygen vacancies. We expect that both anion and cation vacancies near the flat surface act as magnetic defects because of their triplet ground state and Hund's rule. The theoretical forecasts are waiting for experimental justification allowing for the number of the defects in the vicinity of surface is much larger than in the bulk of as-grown samples.     

Coulomb Distortion of Carbododecahedron C20 2+

The electronic structure, geometry, and potential energy surface of the dication of carbododecahedron C₂₀ ²⁺ have been investigated by the PM3 semiempirical method of molecular orbitals. An analog of the Jahn–Teller dynamic effect for this system is revealed, caused by the repulsion of uncompensated positive charges on carbon atoms (Coulomb distortion). The D ₃ symmetry of the ground state of C₂₀ ²⁺ is predicted. The IR vibrational spectrum of the dication of carbododecahedron is calculated, the observation of which could confirm the predicted effect. Evaluational calculations of C₂₀ ⁺ and C₂₀ are also carried out.