A theoretical study of FeNC in the Δ electronic ground state

We report an ab initio calculation, at the MR-SDCI + Q + E_rel/[Roos ANO (Fe), aug-cc-pVQZ (C, N)] level of theory, of the potential energy surface for ⁶Δ_i FeNC. From the ab initio results, we have computed values for the standard spectroscopic parameters of FeN¹²C and FeN¹³C. Analytical representations of the potential energy surfaces have been fitted through the ab initio points, and the resulting functions have been used for directly solving the rotation-vibration Schrödinger equation by means of the MORBID program and by means of an adiabatic-separation method. For ⁶Δ_i FeNC, our ab initio calculations show that the equilibrium structure is linear with r_e (Fe-N) = 1.9354 Å and r_e (N-C) = 1.1823 Å. We find that the bending potential is very shallow, and the MORBID calculations show that the zero-point averaged structure is bent with the expectation values 〈r (Fe-N)〉 = 1.9672 Å, 〈r(N-C)〉 = 1.1866 Å, and . The experimentally derived bond length r₀ (N-C) = 1.03(8) Å reported for ⁶Δ_i FeNC by Lie and Dagdigian [J. Chem. Phys. 114 (2001) 2137-2143] is much shorter than the corresponding ab initio r_e-value and the averaged value from MORBID. Our calculations suggest that this discrepancy is caused by the inadequate treatment of the large-amplitude bending motion of ⁶Δ_i FeNC. It would appear that for floppy triatomic molecules such as FeNC, r₀-values have little physical meaning, at least when they are determined with the effects of the large-amplitude bending motion being ignored, i.e., under the assumption that the r₀ structure is linear.     

An ab initio study of the hyperfine structure in the X2 Π electronic state of HCCS–calculation of vibronically averaged components of the anizotropic hyperfine tensor

The results of ab initio calculations of the vibronically averaged components of the anisotropic magnetic hyperfine tensor in the low-lying vibronic species of the X²Π electronic state of the HCCS radical are reported. The electronically averaged hyperfine coupling constants for hydrogen, deuterium, ¹³C and ³³S are obtained as functions of two bending vibrational modes by the density functional theory method. The vibronic wave functions are calculated with the help of a variational approach which takes into account the Renner–Teller effect and spin-orbit coupling. The results of ab initio calculations are compared to the corresponding experimental findings.     

Investigation of the D Π state of NaK by polarisation labelling spectroscopy

Two-colour polarisation labelling experiments measuring the D-X system of NaK have furnished observations of the D ¹Π state of NaK up to v″ = 42. The last observed level is located 7 cm⁻¹ below the Na(3p ²P_3/2) + K(4s) atomic asymptote, 22247.15 cm⁻¹ above the minimum of the electronic ground state, clearly indicating the dissociation products of this state. The vibrational progressions all exhibit irregular intervals, predominantly because of strong interactions with the nearby d ³Π state, which also dissociates to Na(3p) + K(4s) atoms. The polarisation data have been combined with some resolved fluorescence D-X transitions, and analysed by fitting to spectroscopic parameters and to an analytical potential curve. A full deperturbation treatment has not been attempted, but a ‘robust’ weighting scheme has been used to reduce the influence of levels that cannot be properly represented by a single channel model. Parameters determined in a fit to a potential curve include T_e = 20090.18 ± 0.02 cm⁻¹, well depth 2157.0 ± 0.3 cm⁻¹, R_e = 4.1547 ± 0.0002 Å, with an unweighted root mean square error of 0.12 cm⁻¹ for 959 data.     

Approaching the ground state of the kagomé antiferromagnet

Y0.5Ca0.5BaCo4O7 contains kagomé layers of Co ions, whose spins are strongly coupled, with a Curie-Weiss temperature of -2200 K. At low temperature, T=1.2 K, our diffuse neutron scattering study with polarization analysis reveals characteristic spin correlations close to a predicted two-dimensional coplanar ground state with staggered chirality. The absence of three-dimensional long-range antiferromagnetic order indicates negligible coupling between the kagomé layers. The scattering intensities are consistent with high spin S=3/2 states of Co2+ in the kagomé layers and low spin S=0 states for Co3+ ions on interlayer sites. Our observations agree with previous Monte Carlo simulations indicating a ground state of effectively short range, staggered chiral spin order.     

Determination of the population of the A 3Σu electronic state of nitrogen molecules in a glow-discharge plasma

Results on determining the population of the A ³Σ_u electronic state of N₂ molecules in a gas discharge using a relatively simple spectroscopic technique are reported. The technique proposed can be used not only in pure N₂, but also in nitrogen-containing gas mixtures. The populations of the metastable and nonequilibrium B ³Π_g states of nitrogen molecules are determined. It is shown that the electron-impact excitation is a dominant mechanism for populating the B ³Π_g state.     

The high-resolution spectrum of the ν1 + ν2 band of NO2: A spin-induced perturbation in the ground state

The spectrum of the ν₁ + ν₂ band of NO₂ has been studied with a resolution of 0.025 cm⁻¹. Spin-rotation constants and rotational constants are reported. An interesting perturbation has been found in the ground state of the molecule which occurs when the K_a = 0 and K_a = 2 levels become accidentally nearly degenerate around N = 42. An explanation of this interaction is presented.     

g-factors in the ground state and in the γ-bands in 160,162,164Dy

The g-factors of some members of the ground state band and of the 2⁺ state in the %-vibrational band have been measured in ^160,162,164Dy using the Coulomb Excitation Transient Field technique, induced by ⁵⁸Ni projectiles at 230, 210 and 217 MeV, respectively. The g-factors in the ground state band are consistent with a constant value, while that of the 2⁺_% states is about 20% larger in average than those in the ground state band. Results are discussed in the frame of the systematics in this nuclear region.     

The rotational dependence of the Renner-Teller interaction: a new term in the effective Hamiltonian for linear triatomic molecules in Π electronic states

An additional term in the effective Hamiltonian for a molecule in a ^2S+1Π state subject to a small Renner—Teller effect is derived. It takes the form of a rotational dependence of the Renner—Teller operator and is assigned the parameter ?ω_2,D . This term reproduces two characteristics of the spin—rotational levels of Renner—Teller molecules, both of which are well documented by experimental examples but are not explicable in terms of the previous effective Hamiltonian. These are the small difference between the B values of different vibronic components of the same bending vibrational level and the anomalously strong dependence of the spin—rotation parameter γ on ν₂ for molecules with S > 0. These effects have been explained by previous workers using perturbation theory but in a less general and more complicated fashion.     

The ground state of the Frenkel–Kontorova model

The continual approximation of the ground state of the discrete Frenkel–Kontorova model is tested using a symmetric algorithm of numerical simulation. A “kaleidoscope effect” is found, which means that the curves representing the dependences of the relative extension of an N-atom chain vary periodically with increasing N. Stairs of structural transitions for N ? 1 are analyzed by the channel selection method with the approximation N = ∞. Images of commensurable and incommensurable structures are constructed. The commensurable–incommensurable phase transitions are stepwise.     

Ab initio study of the spectroscopy of the XΠ electronic ground states of CNO and NCO

The X²Π electronic ground states of NCO and CNO have been investigated by complete ab initio methods. The dependence of the Renner-Teller parameters, ? and , on the ab initio method and on the basis set have been studied. These parameters have also been compared to experimental data for NCO. The potential energy surfaces of the X²Π state have been determined by the MRCI method and the cc-pVQZ basis set for NCO and CNO. The rovibronic levels of both isomers have been calculated variationally up to approximatively 4000 cm⁻¹ for J ? 5/2 and K ? 2, with the inclusion of the geometry dependence of the spin-orbit coupling. The agreement with experimental data obtained for NCO is remarkable. A similar accuracy for the ab initio rovibronic levels of CNO is expected since no experimental data exists for this isomer.     

Variational study of the ground state energy of theE−b 1,b 2 Jahn-Teller system

In this paper a variational method for the ground state energy approximation of theE−b ₁,b ₂ Jahn-Teller system is presented. This method is based on the choice of a suitable variational ground state wave function. This trial wave function — a correlated squeezed state — is used to account for the correlation and anharmonicity of the interaction between the two vibrational modes; the anharmonicity of both modes is taken into account by the squeeze effects of these modes. The ground state of mode 1 in this trial wave function is considered as a linear combination of the two displaced harmonic oscillators. The ground state energies for the linearE - e Jahn-Teller system calculated by this method are not only in good agreement with the exact diagonalization results, but they are also better than those from the previous analytical studies. Another conclusion which results from the presented model is the following one: the squeezing effect of mode 1 for the linearE - e Jahn-Teller system is substantially smaller, in contrast with the results which are presented in the previous analytical studies.     

Formation mechanism of hydroxyacetone in glucose pyrolysis: A combined experimental and theoretical study

During fast pyrolysis of biomass, hydroxyacetone (HA, also known as 1-hydroxy-2-propanone) is a vital linear ketone product from fragmentation (ring scission) of cellulose. In this study, density functional theory (DFT) calculations are employed to reveal the HA formation mechanisms and pathways from fast pyrolysis of glucose that is the cellulose-based monosaccharide. Moreover, isotopic labeling fast pyrolysis experiments were conducted to confirm the theoretical calculation results from glucose. The results indicate that during glucose pyrolysis, HA is mainly derived from C1–C2–C3 and C4–C5–C6 segments, with C1 or C6 in the methyl group of HA. The HA from C1–C2–C3 is mainly generated via the 3-ketohexose intermediate, while the formation of the HA from C4–C5–C6 mainly involves the d-fructose intermediate. In addition, the formation of HA is parallel and competitive with the formation of levoglucosan (LG, the most important pyrolytic product of glucose), and the secondary decomposition of LG will result in trace of the HA from C4–C5–C6.     

On experimental tests of D-states in the 3He3H ground state

Recent experiments relevant for D-state components in the ground state of the A = 3 systems are discussed in a simple scheme. This displays the close connection between the tensor force and the D-state components and allows one to interpret the experimental results in a transparent way. Suggestions for a complete experimental test of the D-state are given.     

Measurement of the strong-interaction shift and broadening of the ground state of the pp̄ atom

The K_α X-rays from pp̄ atoms formed in H₂ gas at normal temperature and pressure are unambiguously identified by coincidences with L X-rays populating the 2P level. Background due to inner bremsstrahlung is suppressed by selecting events annihilating into neutral final states only. The K_α line is observed with a significance of more than 25 standard deviations at an energy of 8.67 (15) keV. From fits to the K_α line we obtain a strong-interaction shift and width of the 1S level, averaged over the unresolved spin singlet and triplet contributions, of ΔE + iΓ/2 = [−0.70(15) + i0.80(20)] keV.     

The theoretical study on the potential energy curve for X~3△ state of TiO molecule

This paper applies the density functional theory method to optimise the structure for X ³Δ state of TiO molecule with the basis sets 6-31G, 6-31++G and 6-311G^**. Comparing the attained results with the experiments, it obtains the conclusion that the basis set 6-31++G is most suitable for the optimal structure calculations of X ³Δ state of TiO molecule. The whole potential energy curve for the electronic state is further scanned by using B3P86/6-31++G method for the ground state, then it uses a least square fitted to Murrell--Sorbie functions, at last it calculates the spectroscopic constants and force constants, which are in better agreement with the experimental data.     

A theoretical study of rotational-vibrational levels of the lower two 2Σ+ states of the CaH molecule

Computation of the rotational vibrational levels of the X²Σ⁺ and B²Σ⁺ states of the CaH molecule is carried out by using the adiabatic potential curves obtained by an ab initio SCF-CI calculation (N. Honjou, M. Takagi, M. Makita, and K. Ohno, J. Phys. Soc. Japan 50, 2095–2100 (1981)). Due to two minima in the adiabatic potential curve of the B²Σ⁺ state, an irregularity is found in the rotational-vibrational levels.