A systematic construction of configuration interaction wavefunctions in the complete CI space

Andrew W. Prentice, Jeremy P. Coe, Martin J. Paterson

Research output: Contribution to journalArticle

Abstract

We introduce a systematic approach to construct configuration interaction (CI) wavefunctions through a variant of the Monte Carlo CI (MCCI) method termed systematic-MCCI. Within this approach, the entire interacting space is systematically considered in batches, with the most important configurations across all batches becoming potential additions to the wavefunction. We compare this method to MCCI and a novel pruned-full configuration interaction (FCI) approach. For the ground state of neon, as described by the cc-pVTZ basis, we observe no apparent difference between systematic-MCCI, pruned-MCCI, and MCCI, with all recovering 99% of the correlation energy and producing a very similar wavefunction composition. We then consider the potential energy surface corresponding to the symmetric double hydrogen dissociation of water within a cc-pVDZ basis. Once again MCCI performs comparably to the systematic approaches. Despite systematic-MCCI having longer run times across the number of processors considered, we do observe very good scalability. We then extend this comparison to the first A 1 excited energy of carbon monoxide using the cc-pVDZ basis where the MCCI methods perform similarly, approximating this aforementioned energy to within 0.1 eV despite vast reduction in the wavefunction size. Finally, we consider the chromium dimer with the cc-pVTZ basis and 18 frozen orbitals. Here, we find that the systematic approach avoids being trapped in the same local minimum of configuration space as MCCI, yet MCCI can reach a lower energy by repeating the calculation with more processors.

Original languageEnglish
Article number164112
Number of pages14
JournalThe Journal of Chemical Physics
Volume151
Issue number16
Early online date25 Oct 2019
DOIs
Publication statusPublished - 28 Oct 2019

Fingerprint

Wave functions
configuration interaction
central processing units
Neon
Potential energy surfaces
energy
Chromium
Carbon Monoxide
configurations
neon
Dimers
carbon monoxide
Ground state
Monte Carlo method
Scalability
Hydrogen
chromium
Monte Carlo methods
potential energy
dimers

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

@article{ad43717ed4804ed99bb21b7601a610c4,
title = "A systematic construction of configuration interaction wavefunctions in the complete CI space",
abstract = "We introduce a systematic approach to construct configuration interaction (CI) wavefunctions through a variant of the Monte Carlo CI (MCCI) method termed systematic-MCCI. Within this approach, the entire interacting space is systematically considered in batches, with the most important configurations across all batches becoming potential additions to the wavefunction. We compare this method to MCCI and a novel pruned-full configuration interaction (FCI) approach. For the ground state of neon, as described by the cc-pVTZ basis, we observe no apparent difference between systematic-MCCI, pruned-MCCI, and MCCI, with all recovering 99{\%} of the correlation energy and producing a very similar wavefunction composition. We then consider the potential energy surface corresponding to the symmetric double hydrogen dissociation of water within a cc-pVDZ basis. Once again MCCI performs comparably to the systematic approaches. Despite systematic-MCCI having longer run times across the number of processors considered, we do observe very good scalability. We then extend this comparison to the first A 1 excited energy of carbon monoxide using the cc-pVDZ basis where the MCCI methods perform similarly, approximating this aforementioned energy to within 0.1 eV despite vast reduction in the wavefunction size. Finally, we consider the chromium dimer with the cc-pVTZ basis and 18 frozen orbitals. Here, we find that the systematic approach avoids being trapped in the same local minimum of configuration space as MCCI, yet MCCI can reach a lower energy by repeating the calculation with more processors.",
author = "Prentice, {Andrew W.} and Coe, {Jeremy P.} and Paterson, {Martin J.}",
year = "2019",
month = "10",
day = "28",
doi = "10.1063/1.5123129",
language = "English",
volume = "151",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "16",

}

A systematic construction of configuration interaction wavefunctions in the complete CI space. / Prentice, Andrew W.; Coe, Jeremy P.; Paterson, Martin J.

In: The Journal of Chemical Physics, Vol. 151, No. 16, 164112, 28.10.2019.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A systematic construction of configuration interaction wavefunctions in the complete CI space

AU - Prentice, Andrew W.

AU - Coe, Jeremy P.

AU - Paterson, Martin J.

PY - 2019/10/28

Y1 - 2019/10/28

N2 - We introduce a systematic approach to construct configuration interaction (CI) wavefunctions through a variant of the Monte Carlo CI (MCCI) method termed systematic-MCCI. Within this approach, the entire interacting space is systematically considered in batches, with the most important configurations across all batches becoming potential additions to the wavefunction. We compare this method to MCCI and a novel pruned-full configuration interaction (FCI) approach. For the ground state of neon, as described by the cc-pVTZ basis, we observe no apparent difference between systematic-MCCI, pruned-MCCI, and MCCI, with all recovering 99% of the correlation energy and producing a very similar wavefunction composition. We then consider the potential energy surface corresponding to the symmetric double hydrogen dissociation of water within a cc-pVDZ basis. Once again MCCI performs comparably to the systematic approaches. Despite systematic-MCCI having longer run times across the number of processors considered, we do observe very good scalability. We then extend this comparison to the first A 1 excited energy of carbon monoxide using the cc-pVDZ basis where the MCCI methods perform similarly, approximating this aforementioned energy to within 0.1 eV despite vast reduction in the wavefunction size. Finally, we consider the chromium dimer with the cc-pVTZ basis and 18 frozen orbitals. Here, we find that the systematic approach avoids being trapped in the same local minimum of configuration space as MCCI, yet MCCI can reach a lower energy by repeating the calculation with more processors.

AB - We introduce a systematic approach to construct configuration interaction (CI) wavefunctions through a variant of the Monte Carlo CI (MCCI) method termed systematic-MCCI. Within this approach, the entire interacting space is systematically considered in batches, with the most important configurations across all batches becoming potential additions to the wavefunction. We compare this method to MCCI and a novel pruned-full configuration interaction (FCI) approach. For the ground state of neon, as described by the cc-pVTZ basis, we observe no apparent difference between systematic-MCCI, pruned-MCCI, and MCCI, with all recovering 99% of the correlation energy and producing a very similar wavefunction composition. We then consider the potential energy surface corresponding to the symmetric double hydrogen dissociation of water within a cc-pVDZ basis. Once again MCCI performs comparably to the systematic approaches. Despite systematic-MCCI having longer run times across the number of processors considered, we do observe very good scalability. We then extend this comparison to the first A 1 excited energy of carbon monoxide using the cc-pVDZ basis where the MCCI methods perform similarly, approximating this aforementioned energy to within 0.1 eV despite vast reduction in the wavefunction size. Finally, we consider the chromium dimer with the cc-pVTZ basis and 18 frozen orbitals. Here, we find that the systematic approach avoids being trapped in the same local minimum of configuration space as MCCI, yet MCCI can reach a lower energy by repeating the calculation with more processors.

UR - http://www.scopus.com/inward/record.url?scp=85074229831&partnerID=8YFLogxK

U2 - 10.1063/1.5123129

DO - 10.1063/1.5123129

M3 - Article

VL - 151

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 16

M1 - 164112

ER -