Multi-reference weak pairs local configuration interaction: Efficient calculations of bond breaking

Derek Walter; Emily A. Carter

doi:10.1016/S0009-2614(01)00966-6

Multi-reference weak pairs local configuration interaction: Efficient calculations of bond breaking

Derek Walter, Emily A. Carter

Research output: Contribution to journal › Article › peer-review

44 Scopus citations

Abstract

We present a new local multi-reference singles and doubles configuration interaction (MRSDCI) algorithm. The method presented here eliminates configurations if they involve simultaneous excitations out of widely separated internal orbitals and is therefore based on the weak pairs approximation of Saebø and Pulay. Although the resulting truncated CI expansions have only about 50% as many CSFs as the non-local MRSDCI, we show that they can recover over 99% of the correlation energy. Additionally, we show for the first time that they can accurately describe bond dissociation.

Original language	English (US)
Pages (from-to)	177-185
Number of pages	9
Journal	Chemical Physics Letters
Volume	346
Issue number	1-2
DOIs	https://doi.org/10.1016/S0009-2614(01)00966-6
State	Published - Sep 28 2001
Externally published	Yes

All Science Journal Classification (ASJC) codes

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1016/S0009-2614(01)00966-6

Cite this

@article{139c6a9ed8064c86b50ba3483471e4b1,

title = "Multi-reference weak pairs local configuration interaction: Efficient calculations of bond breaking",

abstract = "We present a new local multi-reference singles and doubles configuration interaction (MRSDCI) algorithm. The method presented here eliminates configurations if they involve simultaneous excitations out of widely separated internal orbitals and is therefore based on the weak pairs approximation of Saeb{\o} and Pulay. Although the resulting truncated CI expansions have only about 50% as many CSFs as the non-local MRSDCI, we show that they can recover over 99% of the correlation energy. Additionally, we show for the first time that they can accurately describe bond dissociation.",

author = "Derek Walter and Carter, {Emily A.}",

note = "Funding Information: D.W. acknowledges Niri Govind, Stuart Watson, Thorsten Kluener, and Frank Starrost for illuminating discussions and technical assistance. D.W. also thanks Wlodiszlaw Duch for providing a copy of his SGGA-CI program for benchmarking purposes. This work was supported by the National Science Foundation via grant #CHE-9970033 to E.A.C. and via a graduate research fellowship to D.W. ",

year = "2001",

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doi = "10.1016/S0009-2614(01)00966-6",

language = "English (US)",

volume = "346",

pages = "177--185",

journal = "Chemical Physics Letters",

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TY - JOUR

T1 - Multi-reference weak pairs local configuration interaction

T2 - Efficient calculations of bond breaking

AU - Walter, Derek

AU - Carter, Emily A.

N1 - Funding Information: D.W. acknowledges Niri Govind, Stuart Watson, Thorsten Kluener, and Frank Starrost for illuminating discussions and technical assistance. D.W. also thanks Wlodiszlaw Duch for providing a copy of his SGGA-CI program for benchmarking purposes. This work was supported by the National Science Foundation via grant #CHE-9970033 to E.A.C. and via a graduate research fellowship to D.W.

PY - 2001/9/28

Y1 - 2001/9/28

N2 - We present a new local multi-reference singles and doubles configuration interaction (MRSDCI) algorithm. The method presented here eliminates configurations if they involve simultaneous excitations out of widely separated internal orbitals and is therefore based on the weak pairs approximation of Saebø and Pulay. Although the resulting truncated CI expansions have only about 50% as many CSFs as the non-local MRSDCI, we show that they can recover over 99% of the correlation energy. Additionally, we show for the first time that they can accurately describe bond dissociation.

AB - We present a new local multi-reference singles and doubles configuration interaction (MRSDCI) algorithm. The method presented here eliminates configurations if they involve simultaneous excitations out of widely separated internal orbitals and is therefore based on the weak pairs approximation of Saebø and Pulay. Although the resulting truncated CI expansions have only about 50% as many CSFs as the non-local MRSDCI, we show that they can recover over 99% of the correlation energy. Additionally, we show for the first time that they can accurately describe bond dissociation.

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U2 - 10.1016/S0009-2614(01)00966-6

DO - 10.1016/S0009-2614(01)00966-6

M3 - Article

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VL - 346

SP - 177

EP - 185

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 1-2

ER -

Multi-reference weak pairs local configuration interaction: Efficient calculations of bond breaking

Abstract

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