Efficient Method for Calculating Effective Core Potential Integrals

Simon C. McKenzie; Evgeny Epifanovsky; Giuseppe M.J. Barca; Andrew T.B. Gilbert; Peter M.W. Gill

doi:10.1021/acs.jpca.7b12679

Efficient Method for Calculating Effective Core Potential Integrals

Simon C. McKenzie
, Evgeny Epifanovsky
, Giuseppe M.J. Barca
, Andrew T.B. Gilbert
, Peter M.W. Gill^*

^*Corresponding author for this work

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

10 Citations (Scopus)

Abstract

Effective core potential (ECP) integrals are among the most difficult one-electron integrals to calculate due to the projection operators. The radial part of these operators may include r⁰, r^-1, and r^-2 terms. For the r⁰ terms, we exploit a simple analytic expression for the fundamental projected integral to derive new recurrence relations and upper bounds for ECP integrals. For the r^-1 and r^-2 terms, we present a reconstruction method that replaces these terms by a sum of r⁰ terms and show that the resulting errors are chemically insignificant for a range of molecular properties. The new algorithm is available in Q-Chem 5.0 and is significantly faster than the ECP implementations in Q-Chem 4.4, GAMESS (US) and Dalton 2016.

Original language	English
Pages (from-to)	3066-3075
Number of pages	10
Journal	Journal of Physical Chemistry A
Volume	122
Issue number	11
DOIs	https://doi.org/10.1021/acs.jpca.7b12679
Publication status	Published - 22 Mar 2018

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title = "Efficient Method for Calculating Effective Core Potential Integrals",

abstract = "Effective core potential (ECP) integrals are among the most difficult one-electron integrals to calculate due to the projection operators. The radial part of these operators may include r0, r-1, and r-2 terms. For the r0 terms, we exploit a simple analytic expression for the fundamental projected integral to derive new recurrence relations and upper bounds for ECP integrals. For the r-1 and r-2 terms, we present a reconstruction method that replaces these terms by a sum of r0 terms and show that the resulting errors are chemically insignificant for a range of molecular properties. The new algorithm is available in Q-Chem 5.0 and is significantly faster than the ECP implementations in Q-Chem 4.4, GAMESS (US) and Dalton 2016.",

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T1 - Efficient Method for Calculating Effective Core Potential Integrals

AU - McKenzie, Simon C.

AU - Epifanovsky, Evgeny

AU - Barca, Giuseppe M.J.

AU - Gilbert, Andrew T.B.

AU - Gill, Peter M.W.

PY - 2018/3/22

Y1 - 2018/3/22

N2 - Effective core potential (ECP) integrals are among the most difficult one-electron integrals to calculate due to the projection operators. The radial part of these operators may include r0, r-1, and r-2 terms. For the r0 terms, we exploit a simple analytic expression for the fundamental projected integral to derive new recurrence relations and upper bounds for ECP integrals. For the r-1 and r-2 terms, we present a reconstruction method that replaces these terms by a sum of r0 terms and show that the resulting errors are chemically insignificant for a range of molecular properties. The new algorithm is available in Q-Chem 5.0 and is significantly faster than the ECP implementations in Q-Chem 4.4, GAMESS (US) and Dalton 2016.

AB - Effective core potential (ECP) integrals are among the most difficult one-electron integrals to calculate due to the projection operators. The radial part of these operators may include r0, r-1, and r-2 terms. For the r0 terms, we exploit a simple analytic expression for the fundamental projected integral to derive new recurrence relations and upper bounds for ECP integrals. For the r-1 and r-2 terms, we present a reconstruction method that replaces these terms by a sum of r0 terms and show that the resulting errors are chemically insignificant for a range of molecular properties. The new algorithm is available in Q-Chem 5.0 and is significantly faster than the ECP implementations in Q-Chem 4.4, GAMESS (US) and Dalton 2016.

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U2 - 10.1021/acs.jpca.7b12679

DO - 10.1021/acs.jpca.7b12679

M3 - Article

SN - 1089-5639

VL - 122

SP - 3066

EP - 3075

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 11

ER -

Efficient Method for Calculating Effective Core Potential Integrals

Abstract

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