Search results for " Quantum chemistry"
showing 10 items of 549 documents
Theoretical and structural studies of lithium cyclic amide conformations. Monomers and aggregates
2000
High level ab initio calculations on the conformations of unsolvated and solvated lithium piperidide, 1, and lithium morpholide, 2, were carried out. It was found that both monomers exhibit a global minimum for a chair structure with a planar nitrogen, and 2 shows an additional stable pseudo boat conformation. Dimers and amine–lithium amide mixed aggregates were also calculated including discrete solvation; the role of aggregation is clearly shown both by the changes in geometries and in the stabilization energies. Semiempirical calculations carried out on a recently synthesized tetrameric mixed aggregate give a geometry very similar to the structure determined by X-ray diffraction. The pre…
Critical analysis of the spin-rotation constants of CF2 and CCl2: A theoretical investigation
2005
Quantum chemical ab initio calculations for the spin-rotation constants of difluorocarbene (CF2) and dichlorocarbene (CCl2) were carried out using coupled-cluster techniques with sequences of correlation-consistent basis sets. Theoretical best estimates were obtained using extrapolation to the complete basis-set limit and taking into account corrections for core correlation, additional diffuse functions and zero-point vibrational effects. It is demonstrated that such accurate theoretical estimates can be used either to support or to challenge the analysis of the experimental spectra and the reliability of the resulting data. 2005 Elsevier B.V. All rights reserved.
Experimental and theoretical studies of Λ doublings and permanent electric dipoles in the low-lying Π1 states of NaCs
2006
We present experimental data on the electric permanent dipole moments d(v',J') and lambda splittings (q factors) in the quasidegenerate (3) 1pi(e/f) state of the NaCs molecule over a wide range of the vibrational (v') and rotational (J') quantum numbers by using the combination of dc Stark mixing and electric radio frequency-optical double resonance methods. Within the experimental (3) 1pi state v' ranged from v' = 0 to 34, q values exhibited a pronounced decrease from 7.91x10(-6) to 0.47x10(-6) cm(-1), while absolute value(d) values varied between 8.0 and 5.0 D. Experimental evaluation yielded small d values about 1 D for D2 1pi state v'3 levels. The experiment is supported by ab initio el…
Ab initio calculations for the far infrared collision induced absorption by N2 gas
2014
We present (far-infrared) Collision Induced Absorption (CIA) spectra calculations for pure gaseous N2 made for the first time, from first-principles. They were carried out using classical molecular dynamics simulations based on ab initio predictions of both the intermolecular potential and the induced-dipole moment. These calculations reproduce satisfactory well the experimental values (intensity and band profile) with agreement within 3% at 149 K. With respect to results obtained with only the long range (asymptotic) dipole moment (DM), including the short range overlap contribution improves the band intensity and profile at 149 K, but it deteriorates them at 296 K. The results show that t…
Conformational investigation of α, β‐dehydropeptides. XI. Molecular and crystal structure of Ac‐(Z )‐ΔPhe‐NMe2 as compared to those of related molecu…
2003
A series of three homologous dimethyldiamides Ac-(Z)-ΔPhe-NMe2, Ac-L-Phe-NMe2 and Ac-DL-Phe-NMe2 have been synthesized and their structures determined from single-crystal X-ray diffraction data. To learn more about the conformational preferences of the compounds studied, the fully relaxed ϕ, ψ conformational energy maps on the free molecules of Ac-ΔAla-NMe2 and Ac-(Z)-ΔPhe-NMe2 were obtained with the HF/3-21G method and the calculated minima re-optimized with the DFT/B3LYP/6-31G** method. The crystal state results have been compared with the literature data. The studied dimethyldiamide Ac-ΔXaa-NMe2 combines the double bond in positions α, β and the C-terminal tertiary amide within one molec…
Interplay of spin-dependent delocalization and magnetic anisotropy in the ground and excited states of [Gd2@C78]− and [Gd2@C80]−
2017
The magnetic properties and electronic structure of the ground and excited states of two recently characterized endohedral metallo-fullerenes, [Gd2@C78]- (1) and [Gd2@C80]- (2), have been studied by theoretical methods. The systems can be considered as [Gd2]5+ dimers encapsulated in a fullerene cage with the fifteen unpaired electrons ferromagnetically coupled into an S = 15/2 high-spin configuration in the ground state. The microscopic mechanisms governing the Gd-Gd interactions leading to the ferromagnetic ground state are examined by a combination of density functional and ab initio calculations and the full energy spectrum of the ground and lowest excited states is constructed by means …
Precision Measurement of the First Ionization Potential of Nobelium
2018
One of the most important atomic properties governing an element's chemical behavior is the energy required to remove its least-bound electron, referred to as the first ionization potential. For the heaviest elements, this fundamental quantity is strongly influenced by relativistic effects which lead to unique chemical properties. Laser spectroscopy on an atom-at-a-time scale was developed and applied to probe the optical spectrum of neutral nobelium near the ionization threshold. The first ionization potential of nobelium is determined here with a very high precision from the convergence of measured Rydberg series to be 6.626 21±0.000 05 eV. This work provides a stringent benchmark for st…
Modelling of silver adhesion on MgO(100) surface with defects
1999
We show how surface defects (especially Fs 0 and Vs 0 centres) can play a major role in the adhesion of Ag (at 1:4 and 1:1 coverages) on the MgO(100) surface. Our calculations use a periodic (slab) model and an ab initio Hartree-Fock approach with a posteriori electron correlation corrections. We are able to analyse the interatomic bond populations, effective charges and multipole moments of ions, in combination with the interface binding energy and the equilibrium distances. Both surface defects cause strong redistributions of the electron density which increase the binding energy of metal atoms by more than an order of magnitude. This implies radiation-induced strengthening of metal adhes…
Theoretical study of the molecular structure and the stability of neutral and reduced tetracyanoethylene
2003
Abstract The molecular structure and the stability of neutral, anionic, and dianionic tetracyanoethylene (TCNE) have been studied with MP2, coupled-cluster (CC), and density functional theory (DFT) procedures. The optimized geometries are in agreement with the available experimental data, although significant deviations for the CN bond distance have been obtained at the MP2 level. The adiabatic electron affinity of TCNE calculated with the B3LYP method is overestimated by 0.32 eV. In the light of the CC results, the source of such an overestimation is suggested to lie on the theoretical approach, rather than on a too low experimental value.
Electronic Properties of Layered Ba0.5Sr0.5TiO3 Heterostructure: Ab initio Hybrid Density Functional Calculations
2005
Ab initio calculations of the BST heterostructure with equiatomic constituent of Sr and Ba species has been carried out within hybrid functional B3PW involving a hybrid of non-local Fock exchange and Becke's gradient corrected exchange functional combined with the non-local gradient corrected correlation potential by Perdew and Wang. The suggested scheme of calculations reproduces experimental lattice parameters of both pure BaTiO3 and SrTiO3. The calculated optical band gap for the pure SrTiO3 (BaTiO3) is 3.56 (3.46) eV (expt. 3.25 and 3.20 eV, respectively), i.e. agreement is much better than in the standard LDA or HF calculations. In the Ba0.5Sr0.5TiO3 solid solution the gap is reduced b…