153 research outputs found
Ab initio many-body calculations on infinite carbon and boron-nitrogen chains
In this paper we report first-principles calculations on the ground-state
electronic structure of two infinite one-dimensional systems: (a) a chain of
carbon atoms and (b) a chain of alternating boron and nitrogen atoms. Meanfield
results were obtained using the restricted Hartree-Fock approach, while the
many-body effects were taken into account by second-order M{\o}ller-Plesset
perturbation theory and the coupled-cluster approach. The calculations were
performed using 6-31 basis sets, including the d-type polarization
functions. Both at the Hartree-Fock (HF) and the correlated levels we find that
the infinite carbon chain exhibits bond alternation with alternating single and
triple bonds, while the boron-nitrogen chain exhibits equidistant bonds. In
addition, we also performed density-functional-theory-based local density
approximation (LDA) calculations on the infinite carbon chain using the same
basis set. Our LDA results, in contradiction to our HF and correlated results,
predict a very small bond alternation. Based upon our LDA results for the
carbon chain, which are in agreement with an earlier LDA calculation
calculation [ E.J. Bylaska, J.H. Weare, and R. Kawai, Phys. Rev. B 58, R7488
(1998).], we conclude that the LDA significantly underestimates Peierls
distortion. This emphasizes that the inclusion of many-particle effects is very
important for the correct description of Peierls distortion in one-dimensional
systems.Comment: 3 figures (included). To appear in Phys. Rev.
Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions
Cooperative effects in two-dimensional cyclic networks containing intermolecular three-centered hydrogen bonding interactions of the type H1&#;A&#;H2 are investigated by means of ab intio molecular orbital and density functional theory calculations. Ring-like clusters consisting of three and up to nine monomers of the cis–cis isomer of carbonic acid H2CO3 are used as basic models, where each unit acts simultaneously as a double hydrogen-bond donor and double hydrogen-bond acceptor. Cooperative effects based on binding energies are evident for (H2CO3)n, where n goes from 2 to 9. Thus, the ZPVE-corrected dissociation energy per bifurcated hydrogen bond increases from 11.52 kcal/mol in the dimer to 20.42 kcal/mol in the nonamer, i.e., a 77% cooperative enhancement. Cooperative effects are also manifested in such indicators as geometries, and vibrational frequencies and intensities. The natural bond orbital analysis method is used to rationalize the results in terms of the substantial charge delocalization taking place in the cyclic clusters. Cooperativity seems close to reaching an asymptotic limit in the largest ring considered, n=9
Towards an effective potential for the monomer, dimer, hexamer, solid and liquid forms of hydrogen fluoride
We present an attempt to build up a new two-body effective potential for
hydrogen fluoride, fitted to theoretical and experimental data relevant not
only to the gas and liquid phases, but also to the crystal. The model is simple
enough to be used in Molecular Dynamics and Monte Carlo simulations. The
potential consists of: a) an intra-molecular contribution, allowing for
variations of the molecular length, plus b) an inter-molecular part, with three
charged sites on each monomer and a Buckingham "exp-6" interaction between
fluorines. The model is able to reproduce a significant number of observables
on the monomer, dimer, hexamer, solid and liquid forms of HF. The shortcomings
of the model are pointed out and possible improvements are finally discussed.Comment: LaTeX, 24 pages, 2 figures. For related papers see also
http://www.chim.unifi.it:8080/~valle
The low-lying excitations of polydiacetylene
The Pariser-Parr-Pople Hamiltonian is used to calculate and identify the
nature of the low-lying vertical transition energies of polydiacetylene. The
model is solved using the density matrix renormalisation group method for a
fixed acetylenic geometry for chains of up to 102 atoms. The non-linear optical
properties of polydiacetylene are considered, which are determined by the
third-order susceptibility. The experimental 1Bu data of Giesa and Schultz are
used as the geometric model for the calculation. For short chains, the
calculated E(1Bu) agrees with the experimental value, within solvation effects
(ca. 0.3 eV). The charge gap is used to characterise bound and unbound states.
The nBu is above the charge gap and hence a continuum state; the 1Bu, 2Ag and
mAg are not and hence are bound excitons. For large chain lengths, the nBu
tends towards the charge gap as expected, strongly suggesting that the nBu is
the conduction band edge. The conduction band edge for PDA is agreed in the
literature to be ca. 3.0 eV. Accounting for the strong polarisation effects of
the medium and polaron formation gives our calculated E(nBu) ca. 3.6 eV, with
an exciton binding energy of ca. 1.0 eV. The 2Ag state is found to be above the
1Bu, which does not agree with relaxed transition experimental data. However,
this could be resolved by including explicit lattice relaxation in the Pariser-
Parr-Pople-Peierls model. Particle-hole separation data further suggest that
the 1Bu, 2Ag and mAg are bound excitons, and that the nBu is an unbound
exciton.Comment: LaTeX, 23 pages, 4 postscript tables and 8 postscript figure
Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions
Theoretical investigation of the excited states dynamics of the polydiacetylene backbone
AN AB INITIO POTENTIAL ENERGY SURFACE AND RO-VIBRATIONAL CALCULATIONS FOR
Author Institution: Herzberg Institute of Astrophysics, National Research Council of Canada; Institut f\""{u}r Theoretische Chemie, and Strahlenchemie, University of ViennaAn ab initio global potential energy surface has been computed for the dimer within the associated coupled pair functional (ACPF) framework using an extended polarized basis set. These 1058 points covering an energy range of up to above the equilibrium have been fitted to a 6D analytical model containing 32 adjustable parameters with a weighted standard deviation of . The global minimum energy path, which is significantly different from that for , and the stationary point geometries and barrier heights have been determined. With this ab intio model, rotational-vibrational calculations, including those using an one-dimensional semi-rigid bender hamiltonial have been performe
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