Search results for "FULL CONFIGURATION INTERACTION"
showing 10 items of 25 documents
The Ground State Electronic Energy of Benzene.
2020
We report on the findings of a blind challenge devoted to determining the frozen-core, full configuration interaction (FCI) ground state energy of the benzene molecule in a standard correlation-consistent basis set of double-$\zeta$ quality. As a broad international endeavour, our suite of wave function-based correlation methods collectively represents a diverse view of the high-accuracy repertoire offered by modern electronic structure theory. In our assessment, the evaluated high-level methods are all found to qualitatively agree on a final correlation energy, with most methods yielding an estimate of the FCI value around $-863$ m$E_{\text{H}}$. However, we find the root-mean-square devia…
High-spin states in tetrahedral X4 clusters (X = H, Li, Na, K)
2010
The high-spin electronic states for lithium, sodium, and potassium four-atom clusters were studied. In particular, we performed coupled cluster geometry optimization of the quintet state in tetrahedral geometry. The quintet state of these systems is characterized by having all the valence electron Unpaired, giving rise to the so-called no-pair bonding. Single-point full configuration interaction computations on the equilibrium geometries for the various Clusters are also presented. The analysis of the valence orbitals in a localized representation confirms the importance of the p atomic orbitals to explain this unusual type of bond. (C) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 110: 8…
The effect of triple excitations in coupled cluster calculations of frequency-dependent polarizabilities
1998
Abstract Frequency-dependent polarizabilities have been implemented within the CC3 model. Comparison with full configuration interaction results shows that the triple excitation effects included in CC3 lead to a significantly improved treatment for the dispersion of the polarizability of CH+. For the refractivity and polarizability anisotropy of N2, better agreement with experiment is found for the CC3 results than for those obtained with the coupled cluster singles and doubles model.
Full configuration-interaction and coupled-cluster calculations of the indirect spin–spin coupling constant of BH
2003
Abstract Full configuration-interaction calculations of the indirect spin–spin coupling constant of the BH molecule have been carried out in order to investigate the performance of various coupled-cluster (CC) methods in the treatment of electron-correlation effects, while the corresponding basis set convergence is analyzed in CC singles and doubles calculations. Assuming additivity of correlation and basis set effects, a theoretical estimate of 50.67 Hz is obtained for the 11 B 1 H spin–spin coupling constant.
Spin-orbit coupling constants from coupled-cluster response theory
2000
A scheme for the calculation of spin-orbit coupling constants using coupled-cluster (CC) electronic structure methods is described based on response-theory expressions for transition properties. An implementation is reported for singlet–triplet transitions within the coupled-cluster singles and doubles (CCSD) approximation. An atomic mean-field representation of the spin-orbit interaction is used to simplify the calculation of spin-orbit coupling constants. Sample calculations are presented for spin-orbit couplings for the 11Σ+→13Π transitions for BH and AlH and for the 11A′→13A″ and the 13A″→11A″ transitions for the silylenes HSiX, X=F, Cl, Br, and are compared to results obtained from ful…
Perturbative treatment of triple excitations in coupled‐cluster calculations of nuclear magnetic shielding constants
1996
A theory for the calculation of nuclear magnetic shielding constants at the coupled‐cluster singles and doubles level augmented by a perturbative correction for connected triple excitations (CCSD(T)) has been developed and implemented. The approach, which is based on the gauge‐including atomic orbital (GIAO) ansatz, is illustrated by several numerical examples. These include a comparison of CCSD(T) and other highly correlated methods with full configuration interaction for the BH molecule, and a systematic comparison with experiment for HF, H2O,NH3, CH4, N2, CO, HCN, and F2. The results demonstrate the importance of triple excitations in establishing quantitative accuracy. Finally, the abil…
Comparison of full-configuration interaction and coupled-cluster harmonic and fundamental frequencies for BH and HF
2001
The harmonic and fundamental frequencies are calculated for the potential-energy curves of BH and HF using the full-configuration interaction model and two hierarchies of coupled-cluster wavefunction models. The anharmonic contributions are also obtained using second-order vibrational perturbation theory. A consistent and systematic improvement is seen for both the harmonic and anharmonic contributions when increasing the level of the correlation treatment. The changes are largest for the harmonic contributions. This is also the case when including valence or diffuse functions in the basis set. Second-order perturbation theory gives a good approximation to the anharmonic contribution and in…
Full Configuration-Interaction Study on the Tetrahedral Li4 Cluster
2008
International audience; The Li4 cluster low lying electronic states were studied. In particular we investigated the tetrahedral geometry at full CI and coupled cluster level, with basis sets of increasing quality. The 5A2 electronic state, characterized by having all the valence electrons unpaired, forming a quite stable no-pair bonding state, was studied in greater detail. In order to compare the energies we also studied the Li4 rhombus singlet ground state. The ability of coupled cluster with perturbative triples to correctly reproduce energy levels in a quasi-degenerate system was validated with respect to the full CI.
Cost-Effective Treatment of Scalar Relativistic Effects for Multireference Systems: A CASSCF Implementation Based on the Spin-free Dirac-Coulomb Hami…
2016
We present an implementation of the complete active space-self-consistent field (CASSCF) method specifically designed to be used in four-component scalar relativistic calculations based on the spin-free Dirac-Coulomb (SFDC) Hamiltonian. Our implementation takes full advantage of the properties of the SFDC Hamiltonian that allow us to use real algebra and to exploit point-group and spin symmetry to their full extent while including in a rigorous way scalar relativistic effects in the treatment. The SFDC-CASSCF treatment is more expensive than its non-relativistic counterpart only in the orbital optimization step, while exhibiting the same computational cost for the rate-determining full conf…
Ground and Excited State First-Order Properties in Many-Body Expanded Full Configuration Interaction Theory
2020
The recently proposed many-body expanded full configuration interaction (MBE-FCI) method is extended to excited states and static first-order properties different from total, ground state correlation energies. Results are presented for excitation energies and (transition) dipole moments of two prototypical, heteronuclear diatomics---LiH and MgO---in augmented correlation consistent basis sets of up to quadruple-$\zeta$ quality. Given that MBE-FCI properties are evaluated without recourse to a sampled wave function and the storage of corresponding reduced density matrices, the memory overhead associated with the calculation of general first-order properties only scales with the dimension of …