Analytical functions for the ground state potential surfaces of C3 (X 1 Σ g+) and HCN (X 1 Σ +)

Analytic functions have been obtained to represent the potential energy surfaces of C3 and HCN in their ground electronic states. These functions closely reproduce the available data on the energy, geometry, and force constants in all stable conformations, as well as data on the various dissociation products, and ab initio calculations of the energy at other conformations. The form of the resulting surfaces are portrayed in various ways and discussed briefly.

Potential energy functions for ground state surfaces of HCO and HNO

Analytical potential functions are reported for the ground state surfaces of HCO and HNO, the functions being derived from spectroscopic and ab initio data. Harmonized force fields have been deduced for the stable configurations of both molecules and vibration frequencies predicted for the metastable species COH and NOH.

Vibrational energy levels for the electronic ground state of the diazocarbene (CNN) molecule

The vibrational energy levels of diazocarbene (diazomethylene) in its electronic ground state, (X) over tilde (3) Sigma(-) CNN, have been predicted using the variational method. The potential energy surfaces of (X) over tilde (3) A" CNN were determined by employing ab initio single reference coupled cluster with single and double excitations (CCSD), CCSD with perturbative triple excitations [CCSD(T)], multi-reference complete active space self-consistent-field (CASSCF), and internally contracted multi-reference configuration interaction (ICMRCI) methods. The correlation-consistent polarised valence quadruple zeta (cc-pVQZ) basis set was used. Four sets of vibrational energy levels determined from the four distinct analytical potential functions have been compared with the experimental values from the laser-induced fluorescence measurements of Wurfel et al. obtained in 1992. The CCSD, CCSD(T), and CASSCF potentials have not provided satisfactory agreement with the experimental observations. In this light, the importance of both non-dynamic (static) and dynamic correlation effects in describing the ground state of CNN is emphasised. Our best theoretical fundamental frequencies at the cc-pVQZ ICMRCI level of theory, v(1) = 1230, v(2) = 394, and v(3) = 1420 cm(-1) are in excellent agreement with the experimental values of v(1) = 1235, v(2) = 396, and v(3) = 1419cm(-1) and the mean absolute deviation between the 23 calculated and experimental vibrational energy levels is only 7.4 cm(-1). It is shown that the previously suggested observation of the v(3) frequency at about 2847cm(-1) was in fact the first overtone 2v(3).

Theoretical rovibrational line intensities in the electronic ground state of ozone

First-principles calculations of absolute line intensities and rovibrational energies of ozone (O-16(3)) are reported using potential energy and electric dipole moment functions calculated by the internally contracted MRCI approach. The rovibrational energies and eigenfunctions (up to about 8500 cm(-1) and J = 64) were obtained variationally with an exact Hamiltonian in internal valence coordinates. More than 4.8 x 10(6) electric dipole transition matrix elements were calculated for the absolute rovibrational line intensities. They are compared with the values of the HITRAN database. The purely rotational absolute line intensities in the (000) state and the rovibrational intensities for the (001)-(000) band agree to within about 0.3 to 1% for the (0 10)-(000) band to within about 3 to 4%. Excellent agreement with experiment is also achieved for low-lying overtone and combination bands. Inconsistencies are found for the (100)-(000) band overlapping with the antisymmetric stretching fundamental and also for the (002)-(000) antisymmetric stretching overtone. The generated dipole moment function can be used for predicting the absorption intensities in any of the heavier isotopomers, hot bands or the rates of spontaneous emission.

Rovibrational energy levels for the electronic ground state of A1OH

The vibrational-rotational energy levels of aluminum monohydroxide in its electronic ground state, (A) over tilde (1)A' AlOH, have been predicted using the variational method. The potential energy surface of the (X) over tilde (1)A' ground state of AlOH was determined employing the ab initio coupled cluster method with single, double, and perturbative triple excitations [CCSD(T)] and the correlation-consistent polarized valence quadruple zeta (cc-pVQZ) basis set. Low-lying J= 0 and J= 1 vibrational levels are reported. These are analyzed in terms of the quasilinearity of the molecule. Coriolis effects are shown to be significant. We hope that our predictions will be of value in the future when assigning rovibrational transitions in spectroscopic studies. (c) 2006 Elsevier B.V. All rights reserved.

Full-dimensional quantum calculations of ground-state tunneling splitting of malonaldehyde using an accurate ab initio potential energy surface

Quantum calculations of the ground vibrational state tunneling splitting of H-atom and D-atom transfer in malonaldehyde are performed on a full-dimensional ab initio potential energy surface (PES). The PES is a fit to 11 147 near basis-set-limit frozen-core CCSD(T) electronic energies. This surface properly describes the invariance of the potential with respect to all permutations of identical atoms. The saddle-point barrier for the H-atom transfer on the PES is 4.1 kcal/mol, in excellent agreement with the reported ab initio value. Model one-dimensional and "exact" full-dimensional calculations of the splitting for H- and D-atom transfer are done using this PES. The tunneling splittings in full dimensionality are calculated using the unbiased "fixed-node" diffusion Monte Carlo (DMC) method in Cartesian and saddle-point normal coordinates. The ground-state tunneling splitting is found to be 21.6 cm(-1) in Cartesian coordinates and 22.6 cm(-1) in normal coordinates, with an uncertainty of 2-3 cm(-1). This splitting is also calculated based on a model which makes use of the exact single-well zero-point energy (ZPE) obtained with the MULTIMODE code and DMC ZPE and this calculation gives a tunneling splitting of 21-22 cm(-1). The corresponding computed splittings for the D-atom transfer are 3.0, 3.1, and 2-3 cm(-1). These calculated tunneling splittings agree with each other to within less than the standard uncertainties obtained with the DMC method used, which are between 2 and 3 cm(-1), and agree well with the experimental values of 21.6 and 2.9 cm(-1) for the H and D transfer, respectively. (C) 2008 American Institute of Physics.

RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297state formulation. This notion is confirmed by the negligible solvatochromism of the intense (ε ≈ 104 M–1cm–1) charge-transfer absorption band in the visible region and by DFT calculations. Oxidation of the compounds occurs mainly at the R-DAB·– radical ligand to produce UV/Vis/NIR and electron paramagnetic resonance (EPR) spectroelectrochemically detectable RuIII species, whereas the reduction proceeds less reversibly and yields predominantly (R-DAB)-ligand-based spin for the 4-methoxyphenyl derivative, measured at low temperature. The results are discussed with respect to metal-to-ligand chargetransfer (MLCT) excited states of conventional (α-diimine)- ruthenium(II) complexes and in view of other (α-diimine)- metal complexes with ambiguous oxidation-state assignments.

Ground-state energy of a classical artificial molecule

We study the ground-state energy of a classical artificial molecule formed by two-dimensional clusters (artificial atoms) of N/2 charged particles separated by a distance d. For the small molecules of N = 2 and 4, we obtain analytical expressions for this energy. For the larger ones, we calculate the ground-state energy using molecular dynamics simulation for N up to 128. From our numerical results, we are able to find out a function to approximate the ground-state energy of the molecules covering the range from atoms to molecules for any inter-atom distance d and for particle number from N = 8 to 128 within a difference less than one percent from the MD data.

Thomas-Fermi ground state of dipolar fermions in a circular storage ring

Recent developments in the field of ultracold gases has led to the production of degenerate samples of polar molecules. These have large static electric-dipole moments, which in turn causes the molecules to interact strongly. We investigate the interaction of polar particles in waveguide geometries subject to an applied polarizing field. For circular waveguides, tilting the direction of the polarizing field creates a periodic inhomogeneity of the interparticle interaction. We explore the consequences of geometry and interaction for stability of the ground state within the Thomas-Fermi model. Certain combinations of tilt angles and interaction strengths are found to preclude the existence of a stable Thomas-Fermi ground state. The system is shown to exhibit different behavior for quasi-one-dimensional and three-dimensional trapping geometries.

Ground state masses and binding energies of the nucleon, hyperon and heavy baryons in a light-front model

The ground state masses and binding energies of the nucleon, lambda0, lambdac+ , lambdab0 are studied within a constituent quark QCD-inspired light-front model. The light-front Faddeev equations for the Qqq composite spin 1/2 baryons, are derived and solved numerically. The experimental data for the masses are qualitatively described by a flavor independent effective interaction.

GROUND-STATE-ENERGY OF SINGULAR POTENTIALS

It is shown that for singular potentials of the form lambda/r(alpha),the asymptotic form of the wave function both at r --> infinity and r --> 0 plays an important role. Using a wave function having the correct asymptotic behavior for the potential lambda/r(4), it is, shown that it gives the exact ground-state energy for this potential when lambda --> 0, as given earlier by Harrell [Ann. Phys. (NY) 105, 379 (1977)]. For other values of the coupling parameter X, a trial basis;set of wave functions which also satisfy the correct boundary conditions at r --> infinity and r --> 0 are used to find the ground-state energy of the singular potential lambda/r(4) It is shown that the obtained eigenvalues are in excellent agreement with their exact ones for a very large range of lambda values.

Bound state solution of the grassmannian nonlinear sigma model with fermions

We construct the S-matrix for bound state (gauge-invariant) scattering for nonlinear sigma models defined on the manifold SU(n) S(U(p)⊗U(n-p)) with fermions. It is not possible to compute gauge non-singlet matrix elements. In the present language, constraints from higher conservation laws determine the bound state solution. An alternative derivation is also presented. © 1988.

Conservation laws for Z(N) symmetric quantum spin models and their exact ground state energies

We derive an infinite set of conserved charges for some Z(N) symmetric quantum spin models by constructing their Lax pairs. These models correspond to the Potts model, Ashkin-Teller model and the particular set of self-dual Z(N) models solved by Fateev and Zamolodchikov [6]. The exact ground state energy for this last family of hamiltonians is also presented. © 1986.

The Ground State Energy per Site of the Quantum and Classical Edwards-Anderson Spin Glass in the Thermodynamic Limit

We derive general rigorous lower bounds for the average ground state energy per site e ((d)) of the quantum and classical Edwards-Anderson spin-glass model in dimensions d=2 and d=3 in the thermodynamic limit. For the classical model they imply that e ((2))a parts per thousand yena'3/2 and e ((3))a parts per thousand yena'2.204a <-.

Ground state properties of neutron-rich Mg isotopes

Studies in regions of the nuclear chart in which the model predictions of properties of nuclei fail can bring a better understanding of the strong interaction in the nuclear medium. To such regions belongs the so called "island of inversion" centered around Ne, Na and Mg isotopes with 20 neutrons in which unexpected ground-state spins, large deformations and dense low-energy spectra appear. This is a strong argument that the magic N = 20 is not a closed shell in this area. In this thesis investigations of isotope shifts of stable 24,25,26Mg, as well as spins and magnetic moments of short-lived 29,31Mg are presented. The successful studies were performed at the ISOLDE facility at CERN using collinear laser and beta-NMR spectroscopy techniques. The isotopes were investigated as single-charged ions in the 280-nm transition from the atomic ground state 2S1/2 to one of the two lowest excited states 2P1/2,3/2 using continuous wave laser beams. The isotope-shift measurements with fluorescence detection for the three stable isotopes show that it is feasible to perform the same studies on radioactive Mg isotopes up to the "island of inversion". This will allow to determine differences in the mean charge square radii and interpret them in terms of deformation. The high detection efficiency for beta particles and optical pumping close to saturation allowed to obtain very good beta-asymmetry signals for 29Mg and 31Mg with half-lives around 1 s and production yields about 10^5 ions/s. For this purpose the ions were implanted into a host crystal lattice. Such detection of the atomic resonances revealed their hyperfine structure, which gives the sign and a first estimate of the value of the magnetic moment. The nuclear magnetic resonance gave also their g-factors with the relative uncertainty smaller than 0.2 %. By combining the two techniques also the nuclear spin of both isotopes could be unambiguously determined. The measured spins and g-factors show that 29Mg with 17 neutrons lies outside the "island of inversion". On the other hand, 31Mg with 19 neutrons has an unexpected ground-state spin which can be explained only by promoting at least two neutrons across the N = 20 shell gap. This places the above nucleus inside the "island". However, modern shell-model approaches cannot predict this level as the ground state but only as one of the low-lying states, even though they reproduce very well the experimental g-factor. This indicates that modifications to the available interactions are required. Future measurements include isotope shift measurements on radioactive Mg isotopes and beta-NMR studies on 33Mg.