Unravelling the visible spectrum of strontium monomethoxide

The bands of the A²E–X²A₁ and B²A₁–X²A₁ electronic transitions of SrO¹²CH₃ and the B²A₁–X²A₁ transition of SrO¹³CH₃ have been recorded at high resolution using a laser ablation jet source. The optical–optical double resonance population depletion technique was used to facilitate the assignment of the spectra. Rotational levels with K = 0, ±1 in the X²A₁ and B²A₁ states and K = 0, 1 and 2 in the A²E state have all been characterised. A perturbation affecting the B²A₁ state caused a reversal of the ordering of the spin-rotation components, F₁ and F₂, in the SrO¹²CH₃ isotopologue. This required the introduction of a modified rotational constant B_mod, affecting only the K = 1, F₂ component of the B²A₁ state, in order to model the SrO¹²CH₃ data in a global fit of the A²E–X²A₁ and B²A₁–X²A₁ transitions.     

Analysis of the fundamental asymmetric stretching mode of T2O

The ν₃ mode of T₂O, observed at 0.04 cm⁻¹, has been analyzed. By an iterative process of fitting and assignment 210 lines were assigned; 167 of these were used in the final fitting. The standard deviation of the fit is 0.023 cm⁻¹. The rotational constants, A, B, and C, as well as the quartic distortion constants, have been evaluated for the excited state.     

The effect of second neighbour repulsion on fcc binary alloy phase diagrams: A Monte Carlo study

We report the results of the Monte Carlo simulation of the phase diagram of fcc binary alloys using a 3-D Ising model with nearest and next-nearest neighbour repulsive interactions. Calculations are carried out for a ratio of second- to first-neighbour interaction energies of 0.4. The resulting phase diagram contains three superstructures A₂B₂, A₂B and A₅B, each separated by a disordered fcc phase. There was no evidence for the formation of an A₃B phase. These results are in qualitative agreement with CVM results.     

Ternary compounds based on binary topological insulators as an efficient way for modifying the Dirac cone

The electronic structure of A^IVB^VI · A₂^VB₃^VI ternary compounds consisting of seven-layer atomic blocks separated by van der Waals gaps has been theoretically investigated. The YbBi(Sb)2Te₄ compounds have been considered, for which a similar atomic structure has been predicted. It has been shown that most compounds based on Group IV elements, as well as YbBi₂Te₄, are three-dimensional topological insulators. Calculations of the surface electronic structure of MBi₂Te₄, where M is a Group IV element or Yb, demonstrate the possibility of tuning the Dirac surface conduction state owing to the first element.     

Extensions of Lieb’s Concavity Theorem

The operator function (A,B)→ Trf(A,B)(K ^*)K, defined in pairs of bounded self-adjoint operators in the domain of a function f of two real variables, is convex for every Hilbert Schmidt operator K, if and only if f is operator convex. We obtain, as a special case, a new proof of Lieb’s concavity theorem for the function (A,B)→ TrA ^p K ^* B ^q K, where p and q are non-negative numbers with sum p+q ≤ 1. In addition, we prove concavity of the operator function

Statistical Mechanical Theory of Bimolecular Reaction. Derivation of the Arrhenius Law. Characterization of a Catalyst

A statistical mechanical theory is developed for gas-phase bimolecular (binary) reactions: AB ⇌ A + B. Based on the activated-complex hypotheses, and expression for the association rate constant k_a is derived: k_a = k*_{AB* → AB} (QAB*/q_A+B), where k*_{AB* →AB} is the rate constant for the transition from the activated state AB* to the molecular state AB, and qx is the equilibrium occupation probability for state X. The three states (AB, AB*, A + B) are defined by three regions of the energyseparation plane for the relative motion of the reactant pair (A, B). If the interatomic potential has a critical barrier ϵ_c at separation r_c and an attractive well with depth ϵ_b (ϵ_c, ϵ_b > k_BT) computations of the q_AB*/q_{A +B} generate an Arrhenius-Boltzmann factor exp (—ϵ_c/k_BT). The virtual rate constant k*_{AB* →AB} is calculated by assuming that the reactant pair reaching the activated state AB* with the separation r < r_c and the energy E > _c moves on to the molecular state AB only if it loses part of its radial kinetic energy with the aid of third body (catalyst or collision) and is trapped by the potential well. With no catalysts present, this constant is approximately given by k*_{AB* →AB} =πd′²v′ R′⁻³, where v′ is the thermal center-of-mass speed, and d′ and R′ are respectively the collision-sphere radius and the mean distance between AB* and any molecule (A, B, AB or AB*). For binary dissociation, the rate constant k_d is given by k_d = k*_{AB* →A+B} q_AB*/q_AB), which generates exp [—(ϵ_c + ϵ_b)/k_BT]. A catalyst for binary reaction is assumed to act as a mediator, facilitating the energy exchange between the radial and rotational modes of motion. Additionally for association only, it also acts as a confinement agent, preventing the pair from flying away from each other. Connections with the collision theory and the activated complex theory are discussed critically.     

Multi-mode ground state interaction terms in C60-based electron donor-acceptor complexes

Quantum-chemical testing of donor-acceptor properties of binary molecular complexes, related to the singlet state, is suggested as QCh calculations of studied systems and their constituents by using both spin-nondependent (RHF) and spindependent (UHF) versions of the exploited computational tool. The avoided crossing of intermolecular interaction terms of neutral moleculesE _int (A ⁰ B ⁰) and molecular ionsE _int (A ⁺ B ⁻) causes a multi-mode character of the ground state term. The dependence of D-A complex properties on the type of the term, space positions of the term minimum, and the interrelation of the corresponding energies are discussed. The suggested approach has been applied to binary complexes C₆₀+X (X=TAE, TDAE, DMMA, COANP, 2Li, Mg).     

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.     

B2C(1A1)和BC2(2A′)的结构与解析势能函数

采用单双取代的二次组态相互作用方法，分别选用6-311++G(d,p)和6-311G(df,pd)基组，对B₂C和BC₂分子的结构进行了优化，得到这两个分子的基态结构为C_2v和C_s，基态电子状态为¹A₁和²A′，同时还得到了它们的平衡几何结构、离解能、谐振频率和力常数. 关键词： 碳化硼 Murrell-Sorbie函数 谐振频率 势能函数     

A theoretical study of the lowest 2 B 1, 2 A 1 and 2 B 2 electronic states in H2S+ and a comparison with corresponding states in related systems

Large scale configuration interaction calculations are employed to study the potential energy surfaces of the three lowest lying states in H₂S⁺. The calculated structural data for the X ² B ₁ and A ² A ₁ states are in very good agreement with previous evidence, but the ² B ₂ state is found to exhibit an [S---H₂]⁺ structure with large SH bond separations and a very small internuclear angle of 32°. Energies and wavefunctions are calculated for all three vibrational modes in the X ² B ₁ and A ² A ₁ excited states of H₂S⁺ and D₂S⁺ and the corresponding Franck-Condon factors for the A ² A ₁-X ² B ₁ band are determined; a maximum in absorption intensity is predicted to occur for v′₂ = 5–6 in H₂S⁺ and for v′₂ = 7–8 in D₂S⁺ for the A ² A ₁-X ² B ₁ transition, for which the calculated T ₀ energy of 18 620 cm^-1 is in excellent agreement with the experimentally determined value of 18 520 cm^-1. Extensive comparison is made with the other AH₂ systems PH₂, NH₂ and H₂O⁺ and trends with respect to geometry, vertical excitation and ionization energies as well as vibrational structure are pointed out; for this purpose the ² B ₂ potential energy curve of PH₂ has also been calculated.     

The AΠu state of : Electric properties, fine and hyperfine coupling constants, and magnetic moments (g-factors). A theoretical study

Several properties are calculated for A²Π_u of —the majority for the first time—including electric and magnetic moments, and fine/hyperfine structure (fs/hfs) parameters. The new results are compared with our previous ones for X² and B² of [P.J. Bruna, F. Grein, J. Mol. Spectrosc. 227 (2004) 67–80]. The electric quadrupole Θ and hexadecapole Φ moments, polarizability α, and hfs constants a, b, c, d, eQq₀, eQq₂ are evaluated at the density functional theory (DFT) level [B3LYP/aug-cc-pVQZ]. The fs constants (spin–orbit coupling A_Π, Λ-doubling p, q, spin-rotation γ_Π), and magnetic moments (g-factors) are obtained via 2nd-order sum-over-states expansions, using wavefunctions and matrix elements obtained with a multireference configuration interaction (MRDCI) method, and the Breit–Pauli Hamiltonian. At equilibrium, 2nd-order properties of A²Π_u are dominated by its coupling with B². For the A state, two independent components are reported for traceless tensor properties (multipoles Θ and Φ; hfs parameters c/d and q₀/q₂) and three for traced properties (polarizability α and g-factors), i.e., one more component than for axially symmetric Σ states. The currently available experimental data on — limited to A_Π, p, and q—are well reproduced by our theoretical results.     

Defect Structure and EPR Parameters of the Cu2+Center in MNB Ternary Glasses

The electron paramagnetic resonance (EPR) parameters (g factors g _//, g _⊥ and hyperfine structure constants A _//, A _⊥) for 15MgO-15Na₂O-69B₂O₃ (MNB):Cu²⁺ ternary glasses were calculated based on the high-order perturbation formulae of 3d⁹ ion in a tetragonal symmetry. From the calculations, the defect structures of MNB:Cu²⁺ ternary glasses were obtained and a negative sign for A _// and A_⊥ for the Cu²⁺ center is suggested in the discussion.     

Probing the electronic structure of the nickel monohalides: Spectroscopy of the low-lying electronic states of NiBr and NiCl

Laser induced fluorescence and single vibronic level emission spectroscopy has been used to probe five low-lying electronic states (X²Π_3/2, A²Δ_5/2, X²Π_1/2, A²Δ_3/2 and B²) of NiBr and NiCl that arise from the 3d⁹ configuration of Ni⁺. Of these, for NiBr only the X²Π_3/2 and A²Δ_5/2 states have been previously observed experimentally, and a complete vibrational analysis of the low-lying states has not been reported for either molecule. In this work, term energies and a complete set of vibrational parameters were derived for all five electronic states for both NiBr and NiCl, and these are compared with recent high level ab initio calculations. In contrast to NiI, there are very few perturbations observed in the vibronic structure of these levels for either NiBr or NiCl. The data set derived in this work affords a detailed analysis of periodic trends in the Nickel monohalide series.     

Relationships between lattice energy and electronic polarizability of AB crystals

The correlations between the electronic polarizability, determined from Clausius-Mosotti equation based on dielectric constant ε, and the lattice energy density u have been established for A^NB^8-N crystals, such as the systems of rock salt crystals (group I-VII, II-VI) and tetrahedral coordinated crystals (group II-VI, III-V). For the A^NB^8-N crystals systems, our present conclusions suggest that lattice energy density u decreases exponentially with increasing electronic polarizability, and the normal mathematical expression between lattice energy density u and electronic polarizability is u = pα^q, p and q depend on the type of crystals. For the same cation binary A^NB^8-N crystals systems, curve fitting equations have been obtained, and the relevant squares of the correlation coefficient R² are larger than 0.99, which show all lattice energy density u are in good exponential relation with electronic polarizability. These empirical equations will give more information on calculating lattice energy or electronic polarizability. New data of lattice energy have been calculated on the above equation u = pα^q, and a good linear trend in the calculating values along with the Zhang’s values has been obtained.     

Cohesive energy of zincblende (A<Superscript>III</Superscript>B<Superscript>V</Superscript> and A<Superscript>II</Superscript>B<Superscript>VI</Superscript>) structured solids

In this paper we present an expression relating the cohesive energy (E _coh in kcal/mol) of A^IIIB^V and A^IIB^VI semiconductors with the product of ionic charges (Z ₁ Z ₂) and nearest-neighbour distance d (Å). The cohesive energy values of these solids exhibit a linear relationship when plotted on a log-log scale against the nearest-neighbour distance d (Å), but fall on different straight lines according to the ionic charge product of the solids. A good agreement has been found between the experimental and calculated values of the cohesive energy of A^IIIB^V and A^IIB^VI semiconductors.     

Applications of photoelectron spectroscopy to molecular propertles: XVIII. The vertlcal ionization potentials of diphosphene as calculated by perturbation corrections to koopmans' theorem

The vertlcal ionization potentials (VIP's) of dimethyl diphosphene have been computed using perturbation corrections to Koopmans' theorem. These corrections allow an estimate of the effects of polarization and correlation, and show for this molecule an important contribution of the specific correlation of the ion for the ²A_g and ²B_u states. The results predict for the first three VIP's the ordering ²A_g, ²A_u, ²B_u, in agreement with our previous assignment.     

Effect of mean-square amplitude of atomic vibrations on the creep behaviour of cubic crystals

Correlation between the activation energyQ of high-temperature creep and the Debye-Waller thermal parameterB, which is proportional to the mean-square amplitude of atomic vibrations, has been examined in the case of 17 faced-centred cubic, body-centred cubic and diamond-structure cubic elements. It is observed thatQ is a function ofB, irrespective of the crystal structure;Q decreases asB increases. The correlation is governed by the power-lawQ=Q ₀(B/B ₀) ^M0 , whereQ ₀=0.095eV andM ₀=−0.62 are numerical constants determined by least-squares fit method, and the constantB ₀=1 nm².     

Quenching of SO2 phosphorescence by a magnetic field

Phosphorescence excitation spectra of the ã³B₁← [Xtilde]¹A₁ transition of SO₂ were measured in the absence and presence of a magnetic field (B = 0?44 T², P(SO₂) = 0?7 Torr). The absorption and phosphorescence excitation spectra of the ã³B₁← [Xtilde]¹A₁ transition of SO₂ measured in the absence of a magnetic field show that the relative intensity of the bands of the phosphorescence excitation spectrum is smaller than the relative intensity of the corresponding bands of the absorption spectrum beginning with the (0, 2, 0) band. In the presence of a magnetic field, the intensity of the phosphorescence excitation band falls, for ν_exc> 26400 cm^-1. Under the direct excitation of the ã³B₁← [Xtilde]¹A₁ transition, the dependence of the magnetic quenching of the SO₂ phosphorescence on the excitation frequency (ν_exc) was studied at P(SO₂) = 0?7 Torr and B = 0?44 T. The dependence of the magnetic field effect on ν_excshows that only the vibrationally excited levels of the ã³B₁ state are sensitive to an external magnetic field. The magnetic field strength and the pressure dependence of the magnetic field effects were studied under indirect excitation of the ã³B₁← [Xtilde]¹A₁ transition at λ_exc = 308 nm. The magnetic field and the pressure dependence were investigated for pure SO₂ and for SO₂ + RH (RH n-C₅H₁₂) mixtures. It was found that the magnetic field effect was saturated at B ? 0?25 T. The saturation value (Gr = l(0?3 T)/l(0)) increases with increasing gas pressure. The magnetic field, the pressure and the excess vibrational energy (ν_excess) dependence of the magnetic quenching of SO2 phosphorescence show that the data observed can be explained by an indirect mechanism within the framework of a low level density approximation.