Error Control and Automatic Detection of Reference Active Spaces in Many-Body Expanded Full Configuration Interaction

被引:1
|
作者
Greiner, Jonas [1 ]
Gauss, Juergen [1 ]
Eriksen, Janus J. [2 ]
机构
[1] Johannes Gutenberg Univ Mainz, Dept Chem, D-55128 Mainz, Germany
[2] Tech Univ Denmark, DTU Chem, DK-2800 Lyngby, Denmark
来源
JOURNAL OF PHYSICAL CHEMISTRY A | 2024年 / 128卷 / 32期
关键词
BASIS-SETS; AB-INITIO; VALENCE; PROBABILITY;
D O I
10.1021/acs.jpca.4c04056
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We present a wide-reaching revamp of the generalized many-body expanded full configuration interaction (MBE-FCI) method. First, we outline how to automatize the selection of reference active spaces, whereby the inherent bias introduced through a manual identification is reduced, also within the context of traditional complete active space methods. Second, we allow for the use of compact orbital clusters as expansion objects, which works to circumvent the unfavorable scaling with the number of orbitals included in the space complementary to the reference orbitals. Finally, we present a new algorithm for ensuring that many-body expansions can be efficiently terminated while conservatively accounting for resulting errors. These developments are all tested on a variety of molecular systems and different orbital representations to illustrate the abilities of our algorithm to produce correlation energies within predetermined error bounds, significantly broadening the overall applicability of the MBE-FCI method.
引用
收藏
页码:6806 / 6818
页数:13
相关论文
共 50 条
  • [1] Many-body expanded full configuration interaction
    Gauss, Juergen
    Eriksen, Janus
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2019, 258
  • [2] Generalized Many-Body Expanded Full Configuration Interaction Theory
    Eriksen, Janus J.
    Gauss, Juergen
    JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2019, 10 (24): : 7910 - 7915
  • [3] Many-Body Expanded Full Configuration Interaction. I. Weakly Correlated Regime
    Eriksen, Janus J.
    Gauss, Juergen
    JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2018, 14 (10) : 5180 - 5191
  • [4] Many-Body Expanded Full Configuration Interaction. II. Strongly Correlated Regime
    Eriksen, Janus J.
    Gauss, Juergen
    JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2019, 15 (09) : 4873 - 4884
  • [5] Ground and excited state first-order properties in many-body expanded full configuration interaction theory
    Eriksen, Janus J.
    Gauss, Juergen
    JOURNAL OF CHEMICAL PHYSICS, 2020, 153 (15):
  • [6] Accelerating Quantum Many-Body Configuration Interaction with Directives
    Cook, Brandon
    Fasano, Patrick J.
    Maris, Pieter
    Yang, Chao
    Oryspayev, Dossay
    ACCELERATOR PROGRAMMING USING DIRECTIVES, WACCPD 2021, 2022, 13194 : 112 - 132
  • [7] On the use of limited configuration interaction for many-body systems
    Hubac, I
    Mach, P
    Wilson, S
    JOURNAL OF PHYSICS B-ATOMIC MOLECULAR AND OPTICAL PHYSICS, 2000, 33 (21) : 4735 - 4746
  • [8] Virtual Orbital Many-Body Expansions: A Possible Route towards the Full Configuration Interaction Limit
    Eriksen, Janus J.
    Lipparini, Filippo
    Gauss, Juergen
    JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2017, 8 (18): : 4633 - 4639
  • [9] Combination of the many-body perturbation theory with the configuration-interaction method
    Dzuba, VA
    Flambaum, VV
    Kozlov, MG
    PHYSICAL REVIEW A, 1996, 54 (05): : 3948 - 3959
  • [10] Embedded configuration interaction theory view of the many-body Kondo state
    Huang, Patrick
    Carter, Emily A.
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2007, 233 : 67 - 67