Generating Coupled Cluster Code for Modern Distributed-Memory Tensor Software.

Using GPU-based HPC platforms efficiently for coupled cluster computations is a challenge due to heterogeneous hardware structures. The constant need to adapt software to these structures and the required man-hours makes the systematization of high-performance code development desirable, even more so for higher-order coupled cluster. This is generally achieved by introducing a high-level representation of the problem, which is then translated into low-level instructions for the hardware using a compiler/translator component.

Highly Accurate Expectation Values Using High-Order Relativistic Coupled Cluster Theory.

This work presents the automatic generation of analytic first derivatives of the energy for general coupled-cluster models using the tenpi toolchain. We report the first implementation of expectation values for CCSDT and CCSDTQ methods within the DIRAC program package for relativistic molecular calculations. As pivotal calculations, we focus on the electric field gradient (EFG) evaluated at the lithium nucleus in LiX (X = H, F, Cl) compounds, enabling the extraction of the nuclear electric quadrupole moment (Li), and at the aluminum nucleus in AlY (Y = H, F, Cl, Br) compounds, for the determination of (Al).

Hilbert space multireference coupled cluster tailored by matrix product states.

In the past decade, the quantum chemical version of the density matrix renormalization group method has established itself as the method of choice for strongly correlated molecular systems. However, despite its favorable scaling, in practice, it is not suitable for computations of dynamic correlation. Several approaches to include that in post-DMRG methods exist; in our group, we focused on the tailored coupled cluster (TCC) approach.

Massively parallel quantum chemical density matrix renormalization group method.

We present, to the best of our knowledge, the first attempt to exploit the super-computer platform for quantum chemical density matrix renormalization group (QC-DMRG) calculations. We have developed the parallel scheme based on the in-house MPI global memory library, which combines operator and symmetry sector parallelisms, and tested its performance on three different molecules, all typical candidates for QC-DMRG calculations. In case of the largest calculation, which is the nitrogenase FeMo cofactor cluster with the active space comprising 113 electrons in 76 orbitals and bond dimension equal to 6000, our parallel approach scales up to approximately 2000 CPU cores.

Toward DMRG-tailored coupled cluster method in the 4c-relativistic domain.

There are three essential problems in computational relativistic chemistry: Electrons moving at relativistic speeds, close lying states, and dynamical correlation. Currently available quantum-chemical methods are capable of solving systems with one or two of these issues. However, there is a significant class of molecules in which all the three effects are present.

Near-Linear Scaling in DMRG-Based Tailored Coupled Clusters: An Implementation of DLPNO-TCCSD and DLPNO-TCCSD(T).

We present a new implementation of density matrix renormalization group based tailored coupled clusters method (TCCSD), which employs the domain-based local pair natural orbital approach (DLPNO). Compared to the previous local pair natural orbital (LPNO) version of the method, the new implementation is more accurate, offers more favorable scaling, and provides more consistent behavior across the variety of systems. On top of the singles and doubles, we include the perturbative triples correction (T), which is able to retrieve even more dynamic correlation.

Quantum information-based analysis of electron-deficient bonds.

Recently, the correlation theory of the chemical bond was developed, which applies concepts of quantum information theory for the characterization of chemical bonds, based on the multiorbital correlations within the molecule. Here, for the first time, we extend the use of this mathematical toolbox for the description of electron-deficient bonds. We start by verifying the theory on the textbook example of a molecule with three-center two-electron bonds, namely, diborane(6).