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Toward a Stochastic Complete Active Space Second-Order Perturbation Theory.

ABSTRACT: In this work, an internally contracted stochastic complete active space second-order perturbation theory, stochastic-CASPT2, is reported. The method relies on stochastically sampled reduced density matrices (RDMs) up to rank four and contractions thereof with the generalized Fock matrix. A new protocol for calculating higher-order RDMs in full configuration interaction quantum Monte Carlo (FCIQMC) has been designed based on (1) restricting sampling of the corresponding excitations to a deterministic subspace, (2) averaging the RDMs from independent dynamics and (3) projecting them onto the closest positive semi-definite matrix. Our protocol avoids previously encountered numerical conditioning problems in the orthogonalization of the perturber overlap matrix stemming from numerical noise. The chromium dimer CASSCF(12,12)/CASPT2 binding curve is computed as a proof of concept.

SUBMITTER: Safari AA

PROVIDER: S-EPMC10788896 | biostudies-literature | 2024 Jan

REPOSITORIES: biostudies-literature

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Toward a Stochastic Complete Active Space Second-Order Perturbation Theory.

Safari Arta A AA Anderson Robert J RJ Manni Giovanni Li GL

The journal of physical chemistry. A 20231228 1

In this work, an internally contracted stochastic complete active space second-order perturbation theory, stochastic-CASPT2, is reported. The method relies on stochastically sampled reduced density matrices (RDMs) up to rank four and contractions thereof with the generalized Fock matrix. A new protocol for calculating higher-order RDMs in full configuration interaction quantum Monte Carlo (FCIQMC) has been designed based on (1) restricting sampling of the corresponding excitations to a determini ...[more]

PMID: 38154124

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Project description:An algorithm to perform stochastic generalized active space calculations, Stochastic-GAS, is presented, that uses the Slater determinant based FCIQMC algorithm as configuration interaction eigensolver. Stochastic-GAS allows the construction and stochastic optimization of preselected truncated configuration interaction wave functions, either to reduce the computational costs of large active space wave function optimizations, or to probe the role of specific electron correlation pathways. As for the conventional GAS procedure, the preselection of the truncated wave function is based on the selection of multiple active subspaces while imposing restrictions on the interspace excitations. Both local and cumulative minimum and maximum occupation number constraints are supported by Stochastic-GAS. The occupation number constraints are efficiently encoded in precomputed probability distributions, using the precomputed heat bath algorithm, which removes nearly all runtime overhead of GAS. This strategy effectively allows the FCIQMC dynamics to a priori exclude electronic configurations that are not allowed by GAS restrictions. Stochastic-GAS reduced density matrices are stochastically sampled, allowing orbital relaxations via Stochastic-GASSCF, and direct evaluation of properties that can be extracted from density matrices, such as the spin expectation value. Three test case applications have been chosen to demonstrate the flexibility of Stochastic-GAS: (a) the Stochastic-GASSCF [5·(6, 6)] optimization of a stack of five benzene molecules, that shows the applicability of Stochastic-GAS toward fragment-based chemical systems; (b) an uncontracted stochastic MRCISD calculation that correlates 96 electrons and 159 molecular orbitals, and uses a large (32, 34) active space reference wave function for an Fe(II)-porphyrin model system, showing how GAS can be applied to systematically recover dynamic electron correlation, and how in the specific case of the Fe(II)-porphyrin dynamic correlation further differentially stabilizes the 3Eg over the 5A1g spin state; (c) the study of an Fe4S4 cluster's spin-ladder energetics via highly truncated stochastic-GAS [4·(5, 5)] wave functions, where we show how GAS can be applied to understand the competing spin-exchange and charge-transfer correlating mechanisms in stabilizing different spin-states.

Project description:The calculation of non-covalent interaction energies on noisy intermediate-scale quantum (NISQ) computers appears to be challenging with straightforward application of existing quantum algorithms. For example, the use of the standard supermolecular method with the variational quantum eigensolver (VQE) would require extremely precise resolution of the total energies of the fragments to provide for accurate subtraction to the interaction energy. Here we present a symmetry-adapted perturbation theory (SAPT) method that may provide interaction energies with high quantum resource efficiency. Of particular note, we present a quantum extended random-phase approximation (ERPA) treatment of the SAPT second-order induction and dispersion terms, including exchange counterparts. Together with previous work on first-order terms (Chem. Sci., 2022, 13, 3094), this provides a recipe for complete SAPT(VQE) interaction energies up to second order, which is a well established truncation. The SAPT interaction energy terms are computed as first-level observables with no subtraction of monomer energies invoked, and the only quantum observations needed are the VQE one- and two-particle density matrices. We find empirically that SAPT(VQE) can provide accurate interaction energies even with coarsely optimized, low circuit depth wavefunctions from a quantum computer, simulated through ideal statevectors. The errors of the total interaction energy are orders of magnitude lower than the corresponding VQE total energy errors of the monomer wavefunctions. In addition, we present heme-nitrosyl model complexes as a system class for near term quantum computing simulations. They are strongly correlated, biologically relevant and difficult to simulate with classical quantum chemical methods. This is illustrated with density functional theory (DFT) as the predicted interaction energies exhibit a strong sensitivity with respect to the choice of functional. Thus, this work paves the way to obtain accurate interaction energies on a NISQ-era quantum computer with few quantum resources. It is the first step in alleviating one of the major challenges in quantum chemistry, where in-depth knowledge of both the method and system is required a priori to reliably generate accurate interaction energies.

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Toward a Stochastic Complete Active Space Second-Order Perturbation Theory.

Publications

Toward a Stochastic Complete Active Space Second-Order Perturbation Theory.

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