Kylin 1.0: An ab-initio density matrix renormalization group quantum chemistry program.

The accurate evaluation of electron correlations is highly necessary for the proper descriptions of the electronic structures in strongly correlated molecules, ranging from bond-dissociating molecules, polyradicals, to large conjugated molecules and transition metal complexes. For this purpose, in this paper, a new ab-initio quantum chemistry program Kylin 1.0 for electron correlation calculations at various quantum many-body levels, including configuration interaction (CI), perturbation theory (PT), and density matrix renormalization group (DMRG), is presented. Furthermore, fundamental quantum chemistry methods such as Hartree-Fock self-consistent field (HF-SCF) and the complete active space SCF (CASSCF) are also implemented. The Kylin 1.0 program possesses the following features: (1) a matrix product operator (MPO) formulation-based efficient DMRG implementation for describing static electron correlation within a large active space composed of more than 100 orbitals, supporting both U 1 n × U 1 S z and U 1 n × SU 2 S symmetries; (2) an efficient second-order DMRG-self-consistent field (SCF) implementation; (3) an externally contracted multi-reference CI (MRCI) and Epstein-Nesbet PT with DMRG reference wave functions for including the remaining dynamic electron correlation outside the large active spaces. In this paper, we introduce the capabilities and numerical benchmark examples of the Kylin 1.0 program.

Mixed-Precision Implementation of the Density Matrix Renormalization Group.

The mixed-precision optimization is an effective emerging technique for quantum chemistry methods to obtain better computational performance and maintain the chemical accuracy. Here, we developed a two-level mixed-precision implementation for the density matrix renormalization group (DMRG) method. This implementation is based on the idea that the DMRG process is an iterative process. Therefore, the first several iteration steps can be executed in single precision. A feasible single-precision DMRG may generate moderate accuracy, and when a few double-precision cleanup sweeps are added, the double-precision accuracy will be recovered. In the double-precision sweeps, we developed a mixed-precision diagonalization method that can run the most time-consuming step in single precision and maintain the double-precision accuracy. By combining these two mixed-precision schemes, we implemented our mixed-precision DMRG method. The benchmark result shows that our mixed-precision implementation achieved a good performance. A speed-up of up to 2.31 is achieved, and the accuracy is preserved within 0.01 kcal/mol.

Stochastic Adaptive Single-Site Time-Dependent Variational Principle.

In recent years, the time-dependent variational principle (TDVP) method based on the matrix product state (MPS) wave function formulation has shown its great power in performing large-scale quantum dynamics simulations for realistic chemical systems with strong electron-vibration interactions. In this work, we propose a stochastic adaptive single-site TDVP (SA-1TDVP) scheme to evolve the bond-dimension adaptively, which can integrate the traditional advantages of both the high efficiency of the single-site TDVP (1TDVP) variant and the high accuracy of the two-site TDVP (2TDVP) variant. Based on the assumption that the level statistics of entanglement Hamiltonians, which originate from the reduced density matrices of the MPS method, follows a Poisson or Wigner distribution, as generically predicted by random-matrix theory, additional random singular values are generated to expand the bond-dimension automatically. Tests on simulating the vibrationally resolved quantum dynamics and absorption spectra in the pyrazine molecule and perylene bisimide (PBI) J-aggregate trimer as well as a spin-1/2 Heisenberg chain show that it can be automatic and as accurate as 2TDVP but reduce the computational time remarkably.

Post-Density Matrix Renormalization Group Methods for Describing Dynamic Electron Correlation with Large Active Spaces.

The ab initio density matrix renormalization group (DMRG) method has been well-established and has become one of the most accurate numerical methods for the precise electronic structure solution of large active spaces. In the past few years, to capture the missing dynamic correlation, various post-DMRG approaches have been proposed through the combination of DMRG and multireference quantum chemical methods or density functional theory. With this in mind, this work provides a brief overview of ab initio DMRG principles and the new developments within post-DMRG methods. For clarity, post-DMRG methods are classified into two main categories depending on whether high-order n-electron reduced density matrices are used, and their merits and disadvantages are properly discussed. Finally, we conclude by discussing unsolved bottlenecks and giving development perspectives of post-DMRG approaches, which are expected to yield quantitative descriptions of complex electronic structures in large strongly correlated molecules and materials.

Low-Scaling Excited State Calculation Using the Block Interaction Product State.

We develop an automatic and efficient scheme for the accurate construction of the bases for excitonic models, which can enable "black-box" excited state structure calculations for large molecular systems. These new and optimized bases, which are named the block interaction product state (BIPS), can be expressed as the direct products of the local states for each chromophore. Each chromophore's local states are selected by diagonalization of its reduced density matrix, which is obtained by quantum chemical calculation of the small subsystem composed of the chromophore and its nearest neighbors. We implemented the BIPS framework with fragment-based calculations considering two- and three-body interactions. Test calculations for eight different molecular aggregates demonstrate that this framework provides an accurate description of not only the excitation energies but also the first-order wave function properties (dipole moment and transition dipole moment) of the low-lying excited states at a low-scaling computational cost.