An adiabatic connection for doubly-occupied configuration interaction wave functions.

An adiabatic connection for doubly-occupied configuration interaction wave functions.

Vu, Nam;Mitxelena, Ion;DePrince, A Eugene;
The Journal of Chemical Physics 2019 Vol. 151 pp. 244121
184
vu2019anthe

Abstract

An adiabatic connection (AC) is developed as an electron correlation correction for doubly occupied configuration interaction (DOCI) wave functions. Following the work of Pernal [Phys. Rev. Lett. 120, 013001 (2018)], the working equations of the approach, termed AC-DOCI, are rooted in the extended random phase approximation (ERPA) and require knowledge of only the ground-state two-electron reduced density matrix (2RDM) from the DOCI. As such, the AC is naturally suited to modeling electron correlation in variational 2RDM (v2RDM)-based approximations to the DOCI. The v2RDM-driven AC-DOCI is applied to the dissociation of molecular nitrogen and the double dissociation of water; the approach yields energies that are similar in quality to those from second-order multireference perturbation theory near equilibrium, but the quality of the AC-DOCI energy degrades at stretched geometries. The exact adiabatic connection path suggests the assumption that the one-electron reduced-density matrix is constant along the AC path is invalid at stretched geometries, but this deficiency alone cannot explain the observed behavior. Rather, it appears that the ERPA's single-particle-transition ansatz cannot, in general, provide good approximations to the 2RDM along the AC path. The AC-DOCI is also applied to a set of 45 reaction energies; for these systems, the approach has an average accuracy that is comparable to that of single-reference second-order many-body perturbation theory.

Citation

ID: 91508
Ref Key: vu2019anthe
Use this key to autocite in SciMatic or Thesis Manager

References

Blockchain Verification

Account:
NFT Contract Address:
0x95644003c57E6F55A65596E3D9Eac6813e3566dA
Article ID:
91508
Unique Identifier:
10.1063/1.5130660
Network:
Scimatic Chain (ID: 481)
Loading...
Blockchain Readiness Checklist
Authors
Abstract
Journal Name
Year
Title
5/5
Creates 1,000,000 NFT tokens for this article
Token Features:
  • ERC-1155 Standard NFT
  • 1 Million Supply per Article
  • Transferable via MetaMask
  • Permanent Blockchain Record
Blockchain QR Code
Scan with Saymatik Web3.0 Wallet

Saymatik Web3.0 Wallet