Ground and excited state polarizabilities and dipole transition properties of benzene from coupled cluster response theory
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…
Hydrogen-Bond Cooperative Effects in Small Cyclic Water Clusters as Revealed by the Interacting Quantum Atoms Approach
The cooperative effects of hydrogen bonding in small water clus- ters (H2O)n (n = 3-6) have been studied by using the partition of the electronic energy in accordance with the interact- ing quantum atoms (IQA) approach. The IQA energy splitting is comple- mented by a topological analysis of the electron density (1(r)) compliant with the quantum theory of atoms-in-mole- cules (QTAIM) and the calculation of electrostatic interactions by using one- and two-electron integrals, thereby avoiding convergence issues inherent to a multipolar expansion. The results show that the cooperative effects of hy- drogen bonding in small water clusters arise from a compromise between: 1) the deformation energ…
Triple excitation effects in coupled cluster calculations of Verdet constants
Abstract The CC3 approach has been employed to calculate the Verdet constants of N 2 ,C 2 H 2 , and CH 4 . For N 2 and C 2 H 2 , relatively large triples contributions are found which need to be included in order to reach close agreement with the experimental constants.
Frequency-dependent polarizabilities and first hyperpolarizabilities of CO and H2O from coupled cluster calculations
Abstract Frequency-dependent electronic polarizabilities and first hyperpolarizabilities for CO and H 2 O have been investigated in coupled-cluster response theory calculations. Triple excitation effects have been considered by means of the CC3 model which has recently been implemented for frequency-dependent polarizabilities and first hyperpolarizabilities. The final estimates for polarizabilities and first hyperpolarizabilities are in good agreement with experimental results.
The Dalton quantum chemistry program system
Dalton is a powerful general-purpose program system for the study of molecular electronic structure at the Hartree-Fock, Kohn-Sham, multiconfigurational self-consistent-field, MOller-Plesset, confi ...
Spin-orbit coupling constants from coupled-cluster response theory
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…
The CC3 model : An iterative coupled cluster approach including connected triples
An alternative derivation of many-body perturbation theory (MBPT) has been given, where a coupled cluster parametrization is used for the wave function and the method of undetermined Lagrange multipliers is applied to set up a variational coupled cluster energy expression. In this variational formulation, the nth-order amplitudes determine the energy to order 2n+1 and the nth-order multipliers determine the energy to order 2n+2. We have developed an iterative approximate coupled cluster singles, doubles, and triples model CC3, where the triples amplitudes are correct through second order and the singles amplitudes are treated without approximations due to the unique role of singles as appro…
The effect of triple excitations in coupled cluster calculations of frequency-dependent polarizabilities
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.
Large-scale calculations of excitation energies in coupled cluster theory: The singlet excited states of benzene
Algorithms for calculating singlet excitation energies in the coupled cluster singles and doubles (CCSD) model are discussed and an implementation of an atomic-integral direct algorithm is presented. Each excitation energy is calculated at a cost comparable to that of the CCSD ground-state energy. Singlet excitation energies are calculated for benzene using up to 432 basis functions. Basis-set effects of the order of 0.2 eV are observed when the basis is increased from augmented polarized valence double-zeta (aug-cc-pVDZ) to augmented polarized valence triple-zeta (aug-cc-pVTZ) quality. The correlation problem is examined by performing calculations in the hierarchy of coupled cluster models…
The electronic spectrum of pyrrole
The electronic spectrum of pyrrole has been investigated by performing calculations using a hierarchy of coupled-cluster models consisting of CCS, CC2, CCSD, and CC3. Basis-set effects have been investigated by carrying out calculations using correlation-consistent basis sets augmented with functions especially designed for the description of Rydberg states. Oscillator strengths, excited state dipole moments, and second moments of the electronic charge distributions have been used to characterize the electronic transitions and final states. Structures and vibrational frequencies have been calculated for a few selected states, and the importance of distinguishing between vertical and adiabat…
Triple excitation effects in coupled-cluster calculations of frequency-dependent hyperpolarizabilities
Abstract We describe an implementation of an analytic scheme for the calculation of static and dynamical first hyperpolarizabilities at the CC3 level in the framework of coupled-cluster response theory. Calculations are reported for the static, the second harmonic generation, and the optical rectification hyperpolarizabilities of FH. The results indicate the importance of triple excitation effects for accurate theoretical predictions of hyperpolarizabilities and lend further support to previous contentions that an experimental value for the second harmonic generation hyperpolarizabilities of FH should be reconsidered.
Accurate Nonlinear Optical Properties for Small Molecules
During the last decade it became possible to calculate by quantum chemical ab initio methods not only static but also frequency-dependent properties with high accuracy. Today, the most important tools for such calculations are coupled cluster response methods in combination with systematic hierarchies of correlation consistent basis sets. Coupled cluster response methods combine a computationally efficient treatment of electron correlation with a qualitatively correct pole structure and frequency dispersion of the response functions. Both are improved systematically within a hierarchy of coupled cluster models. The present contribution reviews recent advances in the highly accurate calculat…
Nuclear magnetic shielding constants in the CC2 model
Abstract Test calculations of nuclear magnetic shielding constants in the CC2 model are performed using the gauge-including atomic orbital approach. Absolute shielding constants are reported for reprsentative first-row hydrides, a few multiply bonded molecules and some challenging cases. The performance of CC2 is analyzed by comparison with experimental data and results from calculations employing more sophisticated treatments of electron correlation. In most cases, CC2 shieldings and chemical shifts are close to those obtained at second-order perturbation theory, despite the fact that the CC2 model includes an approximate treatment of orbital relaxation effects at the correlated level.
The integral‐direct coupled cluster singles and doubles model
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.
Equilibrium geometries of cyclic SiC3 isomers
Equilibrium geometries of two isomers of cyclic SiC3 are determined by both large scale ab initio calculation and a procedure involving the use of experimental data from microwave spectroscopy and calculated harmonic and cubic force fields. Internuclear distances corresponding to structures obtained by both procedures agree to better than 0.003 A in all cases, allowing for precise recommendations of equilibrium structures. Rather large residual inertial defects obtained from moments of inertia based on rotational constants adjusted for effects of vibration–rotation interaction were found to be reduced significantly by inclusion of electronic contributions as estimated from calculations of r…
A coupled cluster study of the 1 1A1g and 1 1B2u states of benzene
A theoretical investigation of the equilibrium structures and harmonic frequencies of the 1 1A1g and 1 1B2u states of benzene is presented. The performance of coupled cluster singles (CCS), the recently proposed CC2 model, and coupled cluster singles and doubles (CCSD) is compared. The CC2 ground and excited states frequencies are a significant improvement of the CCS results and are relatively close to the CCSD results. A comparative analysis of the vibrations in the two electronic states of both C6H6 and C6D6 is presented. The reliability of predicted shifts in harmonic frequencies between the two states and isotopic shifts is estimated on the basis of the convergence in the CCS, CC2, and …