Search results for "coupled cluster"
showing 10 items of 175 documents
Analytic first derivatives for a spin-adapted open-shell coupled cluster theory: Evaluation of first-order electrical properties
2014
An analytic scheme is presented for the evaluation of first derivatives of the energy for a unitary group based spin-adapted coupled cluster (CC) theory, namely, the combinatoric open-shell CC (COSCC) approach within the singles and doubles approximation. The widely used Lagrange multiplier approach is employed for the derivation of an analytical expression for the first derivative of the energy, which in combination with the well-established density-matrix formulation, is used for the computation of first-order electrical properties. Derivations of the spin-adapted lambda equations for determining the Lagrange multipliers and the expressions for the spin-free effective density matrices for…
Ground and excited state polarizabilities and dipole transition properties of benzene from coupled cluster response theory
1999
Abstract The electronic properties and transition properties have been investigated for the lowest singlet electronic states of benzene using coupled cluster response theory. The polarizabilities have been calculated for the ground state and the 1 1 B 2u , 1 1 B 1u 1 1 E 1u and 2 1 E 1u excited states. The dipole allowed transitions out of these states have also been calculated and discussed in the context of the calculated polarizabilities. Oscillator strengths and the second electronic moments of the charge distributions have been used to characterize and identify qualitative features of the individual states. The performance of coupled cluster singles (CCS), the recently proposed CC2 mod…
Theoretical Study on the Structures and Electronic Spectra of TCNE2−
2006
Investigations into the charge-separated states and electron-transfer transitions in tetracyanoethylene (TCNE) compiles have recently generated much interest. In this work we present theoretical calculations showing that the most stable structure of the dianion TCNE 2- has D 2d symmetry in vacuum as well as in the solvents dichloromethane and cicetonitrile. By means of the coupled cluster linear response, we compute the vertical electronic spectrum in both the gas phase and solution. The theoreitcal results, are compared to the experimental data and good agreement is achieved.
Multireference equation-of-motion coupled cluster theory.
2012
A generalization of the equation-of-motion coupled cluster theory is proposed, which is built upon a multireference parent state. This method is suitable for a number of electronic states of a system that can be described by similar active spaces, i.e., different linear combinations of the same set of active space determinants. One of the suitable states is chosen as the parent state and the dominant dynamical correlation is optimized for this state using an internally contracted multireference coupled cluster ansatz. The remaining correlation and orbital relaxation effects are obtained via an uncontracted diagonalization of the transformed Hamiltonian, Ĥ = e(-T) Ĥe(T), in a compact multire…
Improved embedded molecular cluster model
2002
We demonstrate that boundary effects (i.e., displacements of the cluster boundary atoms from their lattice sites and the difference between effective charges of the perfect crystal atoms and those of the cluster atoms in the case of a cluster with no point defect in it) in an embedded molecular cluster (EMC) model can be radically reduced. A new embedding scheme is proposed. It includes search for the structural elements (SE) of which perfect crystal is composed, use of corresponding to these SE expression for the total energy, and application of the degree of localization of equations consistent with the wave functions of the cluster. To get equations for the cluster wave functions, the pr…
State-specific multireference coupled-cluster theory
2012
The multireference problem is considered one of the great challenges in coupled-cluster (CC) theory. Most recent developments are based on state-specific approaches, which focus on a single state and avoid some of the numerical problems of more general approaches. We review various state-of-the-art methods, including Mukherjee's state-specific multireference coupled-cluster (Mk-MRCC) theory, multireference Brillouin–Wigner coupled-cluster (MR-BWCC) theory, the MRexpT method, and internally contracted multireference coupled-cluster (ic-MRCC) theory. Related methods such as extended single-reference schemes [e.g., the complete active space coupled-cluster (CASCC) theory] and canonical transfo…
CCSD-CTOCD static dipole shielding polarizability for quantification of the chiral NMR effects in oxaziridine derivatives
2014
Chiral discrimination by nuclear magnetic resonance (NMR) spectroscopy might be achieved through the pseudo-scalar derived from the dipole shielding polarizability tensor. Coupled Cluster Singles and Doubles-Quadratic Response (CCSD-QR) calculations inside the continuous translation of the origin of the current density formalism have been carried out to determine the effects of basis set, electron correlation, and gauge translation on the determination of this magnitude in oxaziridine derivatives. Inclusion of electronic correlation is needed for adequately describing the pseudo-scalar for the heavier nuclei, making CCSD a rigorous and affordable method to compute these high order propertie…
Revisitation of Nonorthogonal Spin Adaptation in Coupled Cluster Theory.
2015
The benefits of what is alternatively called a nonorthogonally spin-adapted, spin-free, or orbital representation of the coupled cluster equations is discussed relative to orthogonally spin-adapted, spin-orbital, and spin-integrated theories. In particular, specific linear combinations of the orbital cluster amplitudes, denoted spin-summed amplitudes, are shown to reduce the number of contractions that must be explicitly performed and to simplify the expressions and their derivation. The computational efficiency of the spin-summed approach is discussed and compared to orthogonally spin-adapted and spin-integrated approaches. The spin-summed approach is shown to have significant computationa…
The integral‐direct coupled cluster singles and doubles model
1996
An efficient and highly vectorized implementation of the coupled cluster singles and doubles (CCSD) model using a direct atomic integral technique is presented. The minimal number of n6processes has been implemented for the most time consuming terms and point group symmetry is used to further reduce operation counts and memory requirements. The significantly increased application range of the CCSD method is illustrated with sample calculations on several systems with more than 500 basis functions. Furthermore, we present the basic trends of an open ended algorithm and discuss the use of integral prescreening. © 1996 American Institute of Physics.
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…