CASPT2 study on low-lying states of HBS+ and HSB+ cations

Some low-lying states of the nine-valence-electron systems HBS⁺ and HSB⁺ cations have been studied by large-scale theoretical calculations using three methods CASSCF, CASPT2, and DFT B3LYP with the contracted atomic natural orbital and cc-pVTZ basis sets. The geometries of all stationary points along the potential energy surfaces were optimized and the energies were calculated. The potential energy curves of isomerization reactions between HBS⁺ and HSB⁺ were calculated as a function of HBS bond angle. The calculated results indicated that the ground-state HBS⁺ is linear, while the ground-state HSB⁺ is bent, which is in contradiction to Walsh's rules predicting linear structures for the HXY systems containing 10 or less valency electrons.     

Electronic states of the c is - and trans - H3ONO molecules: a CASPT2 study

The CASPT2 calculations for the S₀, T₁, S₁, T₂, and S₂ states of the cis- and trans-CH₃ONO molecules predict the energy levels and geometries of the cis- and trans-isomers in the different states. The CASPT2 adiabatic (T ₀) and vertical (T _v) excitation energies are in good agreement with available experimental data (for the S₁ cis- and trans-isomers). The CH₃O-NO dissociation potential energy curves were calculated at the CASPT2//CASSCF level, and the CASPT2 calculations were performed for the transition states along the T₁, S₁, and T₂ dissociation paths. For the repulsive S₂ state the calculations predict the T _v values larger than 5.4 eV and dissociation products of CH₃O (1²A″) + NO (X²Π).     

Theoretical study of molecular properties of low-lying electronic excited states of H2O and H2S

Geometries, excitation energies, dipole moments and dipole polarisability tensor components of the ground and four lowest excited states ³ B ₁, ¹ B ₁, ³ A ₂, ¹ A ₂ of the H₂O and H₂S molecules were calculated at the CASSCF, CASPT2, CCSD and CCSD(T) level of approximation. Vertical excitation and equilibrium transition energies of these states, having the Rydberg character, are reported too. Properties of both molecules in the ground and in low lying excited states are compared and discussed from the point of view of their molecular electronic structure. Upon excitation we observe dramatic changes of dipole moments and polarisabilities with respect to the ground state. We stress the change of the polarity of H₂O in all excited states accompanied by the enhancement of the dipole polarisability by an order of magnitude. Large, even if less pronounced, are changes of electric properties of H₂S in its excited states. Dipole moments and dipole polarisabilities of ³ B ₁, ¹ B ₁ states of H₂S and H₂O behave quite analogously in comparison to their respective ground state. The general pattern of properties for both molecules in their ³ A ₂ and ¹ A ₂ excited states is more different due to a pronounced participation of the sulphur d-orbitals in these states of the H₂S molecule.     

The Matrix Isolation Spectrum of the CH2 Ion

For CH₂⁺ molecular ions at 5 K we simulate the infrared absorption spectrum, and tabulate all strong absorption lines from 0 to 16 000 cm⁻¹. We use ab initio potential energy, dipole moment, and transition moment surfaces in conjunction with our program system RENNER, which allows for the Renner-Teller effect and spin-orbit coupling in a full-dimensions calculation. This is done for the purpose of guiding our search for the matrix isolation spectrum; our attempts at finding this spectrum are also described.     

A Theoretical Study of ãA2 CH2

The potential energy surface and dipole moment surfaces of the ã⁴A₂ electronic state of CH₂⁺ are calculated ab initio using an augmented correlation-consistent polarized valence quadruple-ζ (aug-cc-pVQZ) basis set, with the incorporation of dynamical correlation using the coupled cluster method with single and double excitations and perturbatively connected triple excitations [CCSD(T)]. We use these surfaces in the MORBID program system to calculate rotation and rotation-vibration term values for ã-state CH₂⁺, CD⁺₂, and CHD⁺ and to simulate the rotation and rotation-vibration absorption spectrum of CH₂⁺ in the ã⁴A₂ electronic state. Our work is motivated by studies of CH₂⁺ that use the Coulomb explosion imaging technique and by the goal of predicting spectra that may be obtained from discharge sources. Although the ã state is the lowest-lying excited state above the X?/Ã ground state pair, it turns out to be relatively high-lying, and we determine that T_e(ã)=30447.5 cm⁻¹. The equilibrium bond angle for ã-state CH₂⁺ is only 77.1°; as a result the asymmetric top κ value is close to 0, and the molecule is equally far from the oblate and prolate symmetric top limits in this electronic state.     

Depth profiling of cells and tissues by using C60 and SF5 as sputter ions

In the present study, SF₅⁺ and C₆₀⁺ were used as primary ions for sputtering and Bi₃⁺ was used as primary ions for analysis. The depth profiling procedure was utilized to make 3D images of the chemistry of single cultured cells and tissue samples of intact intestinal epithelium.The results show sputtering of organic material from cells and tissue with both SF₅⁺ and C₆₀⁺ sources. Cholesterol fragments were found in the superficial layers when sputtering with C₆₀⁺. Spectra were collected revealing the change in yield along the z-axis of the sample. 3D images of the localization of Na, K, phosphocholine and cholesterol were constructed with both ion sources for single cell cultures and the mouse intestine.Cryostate sections of mouse intestine were analysed in 2D and the results were compared with the 3D image of the intestine. The localization of cholesterol and phosphocholine was found to be similar in cryostate sections analysed in two dimensions and the sputtered, freeze-dried intestine analysed in 3D. The comparison of 2D and 3D images suggest that the phosphocholine signal faded with C₆₀⁺ sputtering. In conclusion, both C₆₀⁺ and SF₅⁺ can be used as primary ion sources for sputtering of organic material from cells and tissues. Consecutive analysis with a Bi₃⁺ source can be used to obtain image stacks that could be used for reconstruction of 3D images.     

Theoretical study of the electronic states and transition dipole moments of the LiK molecule

The adiabatic potential energy, the spectroscopic constants and the transition dipole moments of the lowest electronic states of the LiK⁺ molecule, dissociating into Li(2s, 2p, 3s, 3p, 3d, 4s, and 4p) + K⁺ and Li⁺ + K(4s, 4p, 5s, 3d, 5p, 4d, and 6s), have been investigated. We have used an ab initio approach involving a non-empirical pseudopotential for the Li (1s²) and K (1s²2s²2p⁶3s²3p⁶) cores and core valence correlation correction. A very good agreement has been obtained for the ground state for the spectroscopic constants with the available theoretical works. The transition dipole moment from X²Σ, 2²Σ, 3²Σ, and 4²Σ states to higher excited states have been determined. Numerous avoided crossing between electronic states of ²Σ and ²Π symmetries, have been localised and analysed. Their existences are related to the charge transfer process between the two ionic systems Li⁺K and LiK⁺.     

Studies of the electrochemical reduction processes of Bi, HTeO2 and their mixtures

The reduction process of Bi³⁺, HTeO₂⁺ and their mixtures on Au electrode surface was studied by cyclic voltammetry, linear sweep voltammetry, electrochemical impedance spectroscopy and chronoamperometry. XRD and EDS methods were also used to measure the reductive products prepared under different potentials and provide the evidences of the reactions. The results indicate that the reduction of HTeO₂⁺ occurs at more positive potential than that of Bi³⁺, but its reduction rate is slower and adsorption phenomenon exists during its reduction process. Bi₂Te₃ compound can be obtained potentiostatically at a proper potential in all the mixed solutions with concentration ratio CHTe+O₂/CBi3+ in our research range (0.1-10). But pure Bi₂Te₃ compound can only be obtained at 42 mV in the solution with concentration ratio CHTe+O₂/CBi3+ equaling to 1. And the formation of Bi₂Te₃ compound is an inductive co-depositing process: (1) HTeO₂⁺ + 4e⁻ + 3H⁺ → Te⁰ + 2H₂O, (2) 3Te⁰ + 2Bi³⁺ + 6e⁻ → Bi₂Te₃.     

First-principle study on the structural and electronic properties of H2S and SO2 adsorption on Pd-doped MoS2 monolayer

The partial discharge in SF₆-insulated equipment produces characteristic decomposition products: SO₂ and H₂S. The characteristic decomposition products vastly speed up the process of discharge faults. Based on density functional theory (DFT) calculation, single layer Pd-doped MoS₂ (Pd-MoS₂) is adopted as the adsorbent to adsorb SO₂ and H₂S to ensure the operational stability of SF₆-insulated equipment. The adsorption energy, charge transfer and structure parameters of SF₆, H₂S, and SO₂ adsorption on the Pd-MoS₂ monolayer are analysed to find the most stable adsorption structure. The molecular orbital theory, total density of states and partial density of states are studied to analyse the adsorption mechanism. The results show that Pd-MoS₂ adsorbent possesses high catalytic activity and excellent adsorption performance to H₂S and SO₂ by strong chemical adsorption. This study is of great significance to ensure the operational stability of SF6-insulated equipment by removing these characteristic decomposition products.     

Theoretical investigation of the molecular structure and transition dipole moments of the NaK low lying electronic states

The electronic structure and the spectroscopic constants of the low lying electronic states of the NaK⁺ ionic molecule have been determined through using an ab initio approach involving a non-empirical pseudopotential for the Na and K cores and core valence correlation correction. The potential energy of nearly 26 electronic states of ²Σ⁺, ²Π, and ²Δ symmetries has been calculated up to their dissociation limit Na(4d) + K⁺ and Na⁺ + K(6s). Their spectroscopic constants (R_e, D_e, T_e, ω_e, ω_eχ_e, and B_e) are derived and compared with the few available theoretical studies. A good agreement has been found for the ground state and few excited states with previous works. New potential energy curves were presented, for the first time, for the higher excited states. Numerous avoided crossing between electronic states of ²Σ⁺, ²Π symmetries have been localized and analyzed. Their existences are related to the charge transfer between the two ionic molecules Na⁺K and NaK⁺. Furthermore, we have determined the transition dipole moments for several states and analyzed the avoided crossings related to charge transfer between alkaline atoms.     

Ab initio calculation of electronic transition moments for singlet excited states of the H2 molecule

Ab initio CI electronic dipole transition moments have been calculated for the transitions between singlet states of the hydrogen molecule correlating asymptotically with H(nl)+H(1s) (n=1,2,3). The investigated singlet-singlet transitions include the 30 (n=3) inter-Rydberg transitions and the 32 transitions which may contribute to absorption in the far wings of the Balmer α line of atomic hydrogen perturbed by another hydrogen atom in its ground state. Results are presented for internuclear distances 1.0a₀?R?12a₀. The present results compare well with the previous theoretical calculations available for about half of the transitions treated in the present work. Thirty eight new transitions are presented. Adiabatic potential energies for the and and improved energies for the and states are reported as well.     

Rotational analysis of the (4, 8) band in the A-X system of Cl2

Thirty-four rovibronic spectral lines of the Ω=1/2 component of the (4, 8) band in the A-X system of ³⁵Cl₂⁺ were observed in the range of 16,940-17,010 cm⁻¹, employing optical heterodyne-enhanced velocity modulation spectroscopy. Nonlinear least-squares fitting the effective Hamiltonians results in precise band origin and other molecular constants of the levels involved.     

NaCCH自由基低能电子态的理论研究

采用CASSCF/CASPT2方法研究了NaCCH自由基的低能电子态,在C2v对称性下给出了NaCCH自由基9个低能激发态的几何、组态、CI系数、振子强度、垂直激发能和绝热激发能.研究结果表明,NaCCH自由基的基态X1Σ+几何和转动系数与实验值是一致的;谐振频率与其他理论方法得到的值也符合的很好;HOMO和LUMO轨道的能量间隔为3.80eV,对应着13Σ+的绝热激发能;除13Π外,其它低能激发态均是稳定状态;基态到三重态是自旋禁阻的.     

12CH2F2 and13CH2F2far-infrared lasers: New lines and frequency measurements

We report here the discovery of 13 new far-infrared laser lines from¹²CH₂F₂ and seven new lines from¹³CH₂F₂. Most of the new lines were pumped by high-J lines of the 9R branch of a cw-CO₂ laser. Wavelengths range from 97.6 to 616.18 μm. Frequency, pump offset, relative polarization, and relative intensity were measured for most of the new lines.     

Ground states of the hydrogen molecule and its molecular ion in the presence of a magnetic field using the variational Monte Carlo method

ABSTRACT

By using the variational Monte Carlo (VMC) method, we calculated the 1sσ_g-state energies, the dissociation energies, and the binding energies of the hydrogen molecule and its molecular ion in the presence of an aligned magnetic field regime between 0 and 10?a.u. The present calculations are based on using two types of compact and accurate trial wave functions, which are put forward for consideration in calculating energies in the absence of a magnetic field. The obtained results are compared with the most recent accurate values. We conclude that the applications of the VMC method can be successfully extended to cover the case of molecules under the effect of a magnetic field.