Stochastically accelerated perturbative triples correction in coupled cluster calculations.

We introduce a novel algorithm that leverages stochastic sampling techniques to compute the perturbative triples correction in the coupled-cluster framework. By combining elements of randomness and determinism, our algorithm achieves a favorable balance between accuracy and computational cost. The main advantage of this algorithm is that it allows for the calculation to be stopped at any time, providing an unbiased estimate, with a statistical error that goes to zero as the exact calculation is approached. We provide evidence that our semi-stochastic algorithm achieves substantial computational savings compared to traditional deterministic methods. Specifically, we demonstrate that a precision of 0.5 millihartree can be attained with only 10% of the computational effort required by the full calculation. This work opens up new avenues for efficient and accurate computations, enabling investigations of complex molecular systems that were previously computationally prohibitive.

Focal-point approach with pair-specific cusp correction for coupled-cluster theory.

We present a basis set correction scheme for the coupled-cluster singles and doubles (CCSD) method. The scheme is based on employing frozen natural orbitals (FNOs) and diagrammatically decomposed contributions to the electronic correlation energy, which dominate the basis set incompleteness error (BSIE). As recently discussed in the work of Irmler et al. [Phys. Rev. Lett. 123, 156401 (2019)], the BSIE of the CCSD correlation energy is dominated by the second-order Møller-Plesset (MP2) perturbation energy and the particle-particle ladder term. Here, we derive a simple approximation to the BSIE of the particle-particle ladder term that effectively corresponds to a rescaled pair-specific MP2 BSIE, where the scaling factor depends on the spatially averaged correlation hole depth of the coupled-cluster and first-order pair wavefunctions. The evaluation of the derived expressions is simple to implement in any existing code. We demonstrate the effectiveness of the method for the uniform electron gas. Furthermore, we apply the method to coupled-cluster theory calculations of atoms and molecules using FNOs. Employing the proposed correction and an increasing number of FNOs per occupied orbital, we demonstrate for a test set that rapidly convergent closed and open-shell reaction energies, atomization energies, electron affinities, and ionization potentials can be obtained. Moreover, we show that a similarly excellent trade-off between required virtual orbital basis set size and remaining BSIEs can be achieved for the perturbative triples contribution to the CCSD(T) energy employing FNOs and the (T*) approximation.

A periodic equation-of-motion coupled-cluster implementation applied to F-centers in alkaline earth oxides.

We present an implementation of the equation of motion coupled-cluster singles and doubles (EOM-CCSD) theory using periodic boundary conditions and a plane wave basis set. Our implementation of EOM-CCSD theory is applied to study F-centers in alkaline earth oxides employing a periodic supercell approach. The convergence of the calculated electronic excitation energies for neutral color centers in MgO, CaO, and SrO crystals with respect to the orbital basis set and system size is explored. We discuss extrapolation techniques that approximate excitation energies in the complete basis set limit and reduce finite size errors. Our findings demonstrate that EOM-CCSD theory can predict optical absorption energies of F-centers in good agreement with experiment. Furthermore, we discuss calculated emission energies corresponding to the decay from triplet to singlet states responsible for the photoluminescence properties. Our findings are compared to experimental and theoretical results available in the literature.

Surface science using coupled cluster theory via local Wannier functions and in-RPA-embedding: The case of water on graphitic carbon nitride.

A first-principles study of the adsorption of a single water molecule on a layer of graphitic carbon nitride is reported employing an embedding approach for many-electron correlation methods. To this end, a plane-wave based implementation to obtain intrinsic atomic orbitals and Wannier functions for arbitrary localization potentials is presented. In our embedding scheme, the localized occupied orbitals allow for a separate treatment of short-range and long-range correlation contributions to the adsorption energy by a fragmentation of the simulation cell. In combination with unoccupied natural orbitals, the coupled cluster ansatz with single, double, and perturbative triple particle-hole excitation operators is used to capture the correlation in local fragments centered around the adsorption process. For the long-range correlation, a seamless embedding into the random phase approximation yields rapidly convergent adsorption energies with respect to the local fragment size. Convergence of computed binding energies with respect to the virtual orbital basis set is achieved employing a number of recently developed techniques. Moreover, we discuss fragment size convergence for a range of approximate many-electron perturbation theories. The obtained benchmark results are compared to a number of density functional calculations.

Duality of Ring and Ladder Diagrams and Its Importance for Many-Electron Perturbation Theories.

We present a diagrammatic decomposition of the transition pair correlation function for the uniform electron gas. We demonstrate explicitly that ring and ladder diagrams are dual counterparts that capture significant long- and short-ranged interelectronic correlation effects, respectively. Our findings help to guide the further development of approximate many-electron theories and reveal that the contribution of the ladder diagrams to the electronic correlation energy can be approximated in an effective manner using second-order perturbation theory. We employ the latter approximation to reduce the computational cost of coupled cluster theory calculations for insulators and semiconductors by 2 orders of magnitude without compromising accuracy.

Protecting a Diamond Quantum Memory by Charge State Control.

In recent years, solid-state spin systems have emerged as promising candidates for quantum information processing. Prominent examples are the nitrogen-vacancy (NV) center in diamond, phosphorus dopants in silicon (Si:P), rare-earth ions in solids, and VSi-centers in silicon-carbide. The Si:P system has demonstrated that its nuclear spins can yield exceedingly long spin coherence times by eliminating the electron spin of the dopant. For NV centers, however, a proper charge state for storage of nuclear spin qubit coherence has not been identified yet. Here, we identify and characterize the positively charged NV center as an electron-spin-less and optically inactive state by utilizing the nuclear spin qubit as a probe. We control the electronic charge and spin utilizing nanometer scale gate electrodes. We achieve a lengthening of the nuclear spin coherence times by a factor of 4. Surprisingly, the new charge state allows switching of the optical response of single nodes facilitating full individual addressability.

Encuadre, actitud analítica y contratransferencia / Setting, analytical attitude and counter-transference

El trabajo constituye un conjunto de reflexiones acerca del concepto de encuadre y de su aplicación clínica.Los autores desarrollan una concepción dinánica del encuadre, influido en cada momento del proceso analítico por los aspectos clínicos del vínculo y por lo tanto redefinido en cada situación transferencial. Consideran que el elemento central del encuadre es la actitud analítica del analista, expresada en su postura de atención libremente flotante y su disposición a interpretar. Destacan la vinculación del encuadre con la contratransferencia. El análisis de esta última es una guía que tiene el analista para restablecer lanaturaleza del proceso psicoanalítico cuando se perturba la receptividad analítica. Creen que el proceso de receptividad debe ser discriminado del de comprensión, ya que para el primero es fundamental la tolerancia a la nocomprensión por parte del analista. Los autores comentan dos ejemplos clínicos, destacando el rol del análisis de la contra-transferencia en relación con el establecimiento del encuadre

Encuadre, actitud analítica y contratransferencia / Setting, analytical attitude and counter-transference

El trabajo constituye un conjunto de reflexiones acerca del concepto de encuadre y de su aplicación clínica.Los autores desarrollan una concepción dinánica del encuadre, influido en cada momento del proceso analítico por los aspectos clínicos del vínculo y por lo tanto redefinido en cada situación transferencial. Consideran que el elemento central del encuadre es la actitud analítica del analista, expresada en su postura de atención libremente flotante y su disposición a interpretar. Destacan la vinculación del encuadre con la contratransferencia. El análisis de esta última es una guía que tiene el analista para restablecer lanaturaleza del proceso psicoanalítico cuando se perturba la receptividad analítica. Creen que el proceso de receptividad debe ser discriminado del de comprensión, ya que para el primero es fundamental la tolerancia a la nocomprensión por parte del analista. Los autores comentan dos ejemplos clínicos, destacando el rol del análisis de la contra-transferencia en relación con el establecimiento del encuadre (AU)