A deuteron magnetic resonance study of deuterated hydrazine sulphate

The Urey-Bradley force constants of the fluorosulphate radical in the ground ² A ₂ and the excited ² E electronic states and the fluorosulphate anion in the ground ¹ A ₁ electronic state were calculated using published fundamental frequencies. The analysis was carried out within Wilson's FG formalism and the constants were evaluated by a computer program based on the least-squares-fit method. The normal coordinates and the potential energy distributions were also determined. Results support the assignments of the fundamental frequencies—the ground state values for the radical have so far been obtained only from the analysis of its electronic spectrum.     

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.     

Supertransferred hyperfine interaction in magnetic insulators (I)

Two additive contributions to the supertransferred hyperfine (STHF) interaction are suggested to be taken into account in its semi-quantitative analysis of the N-O-M chain: (i) that of bonding molecular orbitals, (ii) that of antibonding orbitals, by calculation of spin-polarization of s-electrons in the N-ion due to the superexchange interaction with d-electrons of the M-ion. Generalized forms of the operator and angular dependence of the STHF interaction were considered due to the use of irreducible tensor operators to the point O_h group. Analytical expressions for the value of the hyperfine fieldH _STHF at the nucleus of the N-ion induced by the magnetic M-ion (both in non-degenerateA ₁,A ₂ ground states and in degenerateE, T ₁,T ₂ states as well) are derived. The value ofH _STHF is dependent upon the type of the M-ion ground state and the geometry of the N-O-M bond. The value ofH _STHF induced by M-ions ofA ₁,A ₂,E states was shown to depend only on the bond angle , and that ofT ₁,T ₂ states on the combinations sin² cos 2, sin² sin 2. The importance of orbital anisotropy in the STHF interaction is emphasized. The orbital anisotropic contribution toH _STHF is drastically dependent on the ground state and its splitting in the crystalline field of low symmetry: the isotropic contribution is determined mainly by the occupation numbers of thet _2g ande _g subshells.     

Pt-Re small cluster interaction with H2

The interaction of small Pt-Re clusters with H₂ is reported here through ab initio multicon-figuration self-consistent field (MC-SCF) calculations, plus extensive multireference configuration interaction (MR-CI), variational and perturbative calculations. These calculations provide a cluster model for the activation of hydrogen by Pt-Re bimetallic catalysts. It was found that the ⁶S(5d⁵6s²) Re atom ground state needs an important activation to induce very weak capture of separated hydrogen atoms, whereas in the lowest excited states the activation energies are small or zero, with a very reasonable depth of well. The four lowest states of Pt-Re were found to be ⁴ Σ⁺, ⁶Π_yz, ^{Σ +} and ⁶Π_xz. Pt-Re interaction with H₂ has been studied from both metal ‘sides’. It was established that Pt-Re with the platinum side in the ground electronic ⁴Σ⁺ state and in the lowest ⁶Π⁺ excited states is able to capture H₂ molecules without activation, whereas in the ⁶Π_yz and ⁶Π_xz excited states there is no capture. The rhenium side of Pt-Re in its four lowest states considered cannot capture the H₂ molecule. The interaction of Pt₂-Re with H₂ was studied also. For the ground ²B₂ electronic state and the low lying ²A₁ electronic state the platinum moiety can spontaneously capture and break H₂. The rhenium side of Pt₂-Re(B₂), however, can capture H₂ only after surmounting a small barrier, and the excited Pt₂-Re(²A₁) can spontaneously capture H₂. For Pt₂-Re in its low lying ⁴A₁ electronic state both metal sides capture and break H₂ after surmounting a small barrier.     

外场下SnS分子结构及其特性

对S原子采用6-311++G**基组,Sn原子采用SDB-cc-pVTZ基组,利用密度泛函(B3P86)方法对SnS分子进行了基态结构优化,并研究了外场作用下SnS基态分子键长、能量、能级分布、电荷布居分布、谐振频率和红外谱强度的影响规律.然后利用含时密度泛函(TD-B3P86)方法研究了SnS分子在外场下的激发特性.结果表明,在所加的电场范围内(-0.04 a.u.-0.04 a.u.),随着正向电场的增大,分子键长和红外谱强度均是先减小后增大;总能E,SnS基态分子的最高已占据轨道能量EH和谐振频率均是先增大后减小;分子的最低未占空轨道能量EL和能隙Eg均随正向电场的增大而减小.随着正向电场的增大,SnS分子由基态至前9个单重激发态跃迁的波长增大,激发能则减小.     

Unitary equivalence between a spin 1/2 charged particle in a two-dimensional magnetic field and a spin 1/2 neutral particle with an anomalous magnetic moment in a two-dimensional electric field

We prove the unitary equivalence between the Dirac HamiltonianH _D for a relativistic spin 1/2 neutral particle with an anomalous magnetic moment in a two-dimensional electrostatic fieldE = (E ₁,E ₂) and the direct sum of the Dirac-Weyl operatorsD(±A) for a spin 1/2 charged particle in two-dimensional magnetic fields ±dA with the vector potentialA =E ₂ dx ¹ -E ₁ dx ², (x ¹,x ²) ². As applications, we investigate the ground state and the spectra ofH _D.     

EPR spectra of the excited nitrogen state in 6H-SiC

A study is reported of donor EPR spectra in compensated 6H-SiC crystals with donor concentrations (N _D -N _A ) varied from 8×10¹⁷ to 5×10¹⁶ cm^?3, performed within a temperature interval from 77 to 170 K at a frequency of 37 GHz. A second paramagnetic state of nitrogen in silicon carbide has been found to exist, and it is associated with its excited 1S(E) state becoming paramagnetic after thermal ionization of the donor electrons from the 1S(A ₁) to 1S(E) level. The EPR spectrum of nitrogen in the 1S(E) state is a single line with an anisotropic width because of the unresolved hyperfine structure. A light-induced charge transfer between the ground, 1S(A ₁), and excited, 1S(E), nitrogen states has been observed. The valley-orbit splitting and the energy required to ionize donor electrons from the 1S(E) to higher lying excited states have been determined for the cubic nitrogen sites. The parameters of a structural defect, characteristic of n-type 6H-SiC compensated crystals, have been established.     

Pseudo-Jahn–Teller effect in Si4X4 (X = F,Cl, Br,I) molecules: a theoretical investigation

ABSTRACT

The variability of planar rings in Si₄X₄ (X?=?F, Cl, Br, I) molecules caused by the pseudo-Jahn–Teller impact (PJTE) was evaluated as an original PJTE work. Optimisation and the following frequency calculations in these molecules illustrated that in high-symmetry planar (with D_4h symmetry) geometry, all of these compounds were unstable and their structures were puckered to lower C_2h symmetry stable geometry. Furthermore, the vibronic coupling interaction between ¹A_1g ground and the first ¹E_g excited states through (¹A_1g?+?¹E_g) ? e_g PJTE problem was the cause of non-planarity of the four-member ring and the symmetry breaking phenomenon in those series. The calculated gaps (Δ) between the ground state and the E_g excited state, the vibronic coupling (F) and ground state primary force constant values (k₁) were obtained from the numerical fitting of the ground state adiabatic potential energy surface with the analytical expressions of these molecules. Finally, natural bond analysis (NBO) was used for the design of the strongest interaction and natural atomic charges of these structures.     

Methyl and skeletal torsion interaction in methyl thiolfluoroformate

The microwave spectrum of methyl thiolfluoroformate (FCOSCH₃) is reported for the ground state and seven vibrational satellites. The methyl group is in the syn conformation to the carbonyl group. The dipole moment components are μ_a = 2.89(2) D, μ_b = 0.30(8) D, and μ_c = 0. Spacings of A and E levels due to methyl internal rotation are analyzed for the ground state, the first excited methyl torsional state, and the first excited skeletal torsional state. An anomalous sequence of A and E levels occurring in the latter satellite arises from torsional interaction, according to two-dimensional model calculations. Potential parameters consistent with the three observed level separations are V₃ = 304(5) cm⁻¹, V₆ = 23(1) cm⁻¹ for the methyl torsion and either k = 1.912 or k = 2.936 cm⁻¹ deg⁻² for the skeletal torsional force constant.     

Electronic states of C2H6 +

The complete photoelectron spectrum of ethane has been measured in the valence region using Ne, He I, and He II resonance radiation. The resolution of these spectra is sufficient to partially resolve vibronic structure accompanying the transition to the ground ionic state. The similarity of this structure with that obtained from model calculations using the Jahn-Teller theorem strongly suggests that the active vibration in this transition is a doubly degenerate CH₃ deformation mode and that the ground ionic state is a Jahn-Teller split ² E _g state. These experiments suggest a ² A _1g term for the first excited ionic state. The transition to the ² A _2u state of the ion contains evidence for two active vibrations v ₁ (C–H stretch) and v ₃ (C-C stretch).     

Optimized t-expansion method for the Rabi Hamiltonian

A polemic arose recently about the applicability of the t-expansion method to the calculation of the ground state energy E₀ of the Rabi model. For specific choices of the trial function and very large number of involved connected moments, the t-expansion results are rather poor and exhibit considerable oscillations. In this Letter, we formulate the t-expansion method for trial functions containing two free parameters which capture two exactly solvable limits of the Rabi Hamiltonian. At each order of the t-series, E₀ is assumed to be stationary with respect to the free parameters. A high accuracy of E₀ estimates is achieved for small numbers (5 or 6) of involved connected moments, the relative error being smaller than ¹⁰−4 (0.01%) within the whole parameter space of the Rabi Hamiltonian. A special symmetrization of the trial function enables us to calculate also the first excited energy E₁, with the relative error smaller than ¹⁰−2 (1%).     

A global potential energy surface for H2S+(X 4A′′) and quasi-classical trajectory study of the S+(4S) + H2(X1Σ+g) reaction

A novel global potential energy surface for H₂S⁺(X?⁴A″) based on accurate ab initio calculations is presented. Energies are calculated at the multi-reference configuration interaction level with Davidson correction using aug-cc-pVQZ basis set plus core-polarisation high-exponent d functions. A grid of 4552 points is used for the least-square fitting procedure in the frame of a many-body expansion. The topographical features of the new potential energy surface are here discussed in detail. Such a surface is then employed for dynamic studies of the S(⁴S) + H₂(X?¹Σ⁺_g) →SH⁺(X?³Σ^?) + H(²S) reaction using the quasi-classical trajectory method. State specific trajectories are calculated, for both ground and ro-vibrationally excited initial states of H₂(X?¹Σ⁺_g). Corrections to the zero point energy leakage of the classical calculations are also presented. Calculated reaction cross sections and rate constants are here reported and compared with available literature.     

Vacancy formation energies from positron trapping measurements

The threshold temperatureT _t at which thermally generated vacancies produce measurable positron trapping is a linear function of the energy of self-diffusionQ. SinceQ is also linearly related to the vacancy formation energyE _1v ^f , a measurement ofT _t leads directly to a determination of the latter. It is possible to make a precise determination ofE _1v ^f without approaching the melting point—a major advantage in dealing with refractories or with metals having a high vapour pressure in the solid state.     

Linear response in chaotic states of discrete dynamics

The importance of the coupling operatorA of an external disturbance to a 1-dimensional map is discussed. A time dependent susceptibility _t ^BA is introduced describing the linear response in chaotic states observed with observableB. Its properties are given, its temporal decay, and its relation to correlations (fluctuations). Some examples are evaluated explicitely. The static susceptibility depends on the correlation decay as usual, and diverges if the state changes its character under the perturbation.     

BeH2(X1Σ+g)与H2S(X1A1)分子的结构与解析势能函数

运用单双取代二次组态相关(QCISD)方法,在6-311++G(3df,3pd)基组水平上,对BeH₂和H₂S分子的结构进行了优化计算,得到基态BeH₂分子的稳定结构为D_∞h构型,电子态为X¹Σ⁺_g,平衡核间距R_BeH=0.13268nm,R_{关键词： 2}')" href="#">BeH₂ 2S')" href="#">H₂S Murrell-Sorbie函数 多体项展式理论 解析势能函数     

Methyl barrier to internal rotation and evidence of torsion-torsion interaction in methyl thiolcyanoformate

The rotational spectrum of methyl thiolcyanoformate has been measured in the ground state and in four vibrationally excited states. The methyl group has the conformation syn with respect to the carbonyl group. The E component lines were assigned only in the ground state and the methyl group barrier to internal rotation has the value V₃ = 705 ± 20 cal/mole. The A species rotational transitions of the first excited state of the methyl and skeletal torsions do not follow a semirigid-rotor pattern probably because they strongly interact.     

A quasiclassical study of collisions of He with HD(B 1Σ+ u )

A quasiclassical trajectory study has been carried out for collisions of ⁴He with electronically excited H₂(B ¹Σ⁺ _u ) and its isotopomer HD. By using analytical fits for the ab initio potential energy surfaces of the ground and the excited state we have obtained vibrational and electronic quenching cross sections for several initial conditions. We draw the following conclusions. Vibrational excitation strongly promotes electronic quenching whereas translational energy is less effective. Rotational excitation decreases the rate of quenching. In a remarkable contrast to the ground electronic state, vibrational energy transfer on the excited potential energy surface is an efficient and fast process. Collisions at high energies results in T → R energy transfer. The above conclusions are valid for both H₂ and HD.     

Theory of the ionization of ethane

Ab initio molecular orbital studies on C₂H₆ ⁺ support an assignment of ² A _1g (D _3d point group symmetry) for the ground state of this cation. This differs from the prediction of Koopmans' theorem which suggests a ² E_g state for vertical ionization. Approximate force constants and vibrational frequencies are calculated for the ethane cation in the ² A _1g state and are found to be consistent with the vibrational progression observed in the experimental photoelectron spectrum.     

Hydrogen bonding and excited state properties of the photoexcited hydrogen‐bonded (E)‐S‐(2‐aminopropyl) 3‐(4‐hydroxyphenyl)prop‐2‐enethioate complexes

The time‐dependent density functional theory (TDDFT) method has been performed to investigate the excited state and hydrogen bonding dynamics of a series of photoinduced hydrogen‐bonded complexes formed by (E)‐S‐(2‐aminopropyl) 3‐(4‐hydroxyphenyl)prop‐2‐enethioate with water molecules in vacuum. The ground state geometric optimizations and electronic transition energies as well as corresponding oscillator strengths of the low‐lying electronic excited states of the (E)‐S‐(2‐aminopropyl) 3‐(4‐hydroxyphenyl)prop‐2‐enethioate monomer and its hydrogen‐bonded complexes O₁‐H₂O, O₂‐H₂O, and O₁O₂‐(H₂O)₂ were calculated by the density functional theory and TDDFT methods, respectively. It is found that in the excited states S₁ and S₂, the intermolecular hydrogen bond formed with carbonyl oxygen is strengthened and induces an excitation energy redshift, whereas the hydrogen bond formed with phenolate oxygen is weakened and results in an excitation energy blueshift. This can be confirmed based on the excited state geometric optimizations by the TDDFT method. Furthermore, the frontier molecular orbital analysis reveals that the states with the maximum oscillator strength are mainly contributed by the orbital transition from the highest occupied molecular orbital to the lowest unoccupied molecular orbital. These states are of locally excited character, and they correspond to single‐bond isomerization while the double bond remains unchanged in vacuum.     

Rotational structure of the origin band in the 1A′ ←X1σ+ electronic transition of C4H− and C4D−

The rotational structure of the origin band for the ¹A′←X¹σt⁺ electronic transition, lying just below the electron affinity of C⁴H, was recorded by means of a two-colour resonant photodetachment technique. This allowed a determination of the rotational constants in the X¹σt⁺ ground and ¹A′ dipole bound excited state. The low lying A²II excited state of C⁴H is inferred to be the parent of the dipole bound state. The excited electronic state is deduced to have a nonlinear planar structure whereas the ground is linear according to the spectral analysis. The rotational constants have been obtained: B′; = 0.1552(2)cm^?1 for the X¹σt⁺ state, and A′ = 30.73(1), B′ = 0.1587(2), C′ = 0.1581(2)cm^?1 for the ¹A′ state.