TY - JOUR

T1 - Density fitting and Cholesky decomposition of the two-electron integrals in local multireference configuration interaction theory

AU - Krisiloff, David B.

AU - Krauter, Caroline M.

AU - Ricci, Francis J.

AU - Carter, Emily A.

PY - 2015/11/10

Y1 - 2015/11/10

N2 - To treat large molecules with accurate ab initio quantum chemistry, reduced scaling correlated wave function methods are now commonly employed. Optimization of these wave functions in practice requires some approximation of the two-electron integrals. Both Cholesky decomposition (CD) and density fitting (DF) are widely used approaches to approximate these integrals. Here, we compare CD and DF for use in local multireference singles and doubles configuration interaction (LMRSDCI). DF-LMRSDCI provides less accurate total energies than CD-LMRSDCI, but both methods are accurate for energy differences. However, DF-LMRSDCI is significantly less computationally expensive than CD-LMRSDCI on the molecules tested, suggesting that DF-LMRSDCI is an efficient, often sufficiently accurate alternative to our previously reported CD-LMRSDCI method.

AB - To treat large molecules with accurate ab initio quantum chemistry, reduced scaling correlated wave function methods are now commonly employed. Optimization of these wave functions in practice requires some approximation of the two-electron integrals. Both Cholesky decomposition (CD) and density fitting (DF) are widely used approaches to approximate these integrals. Here, we compare CD and DF for use in local multireference singles and doubles configuration interaction (LMRSDCI). DF-LMRSDCI provides less accurate total energies than CD-LMRSDCI, but both methods are accurate for energy differences. However, DF-LMRSDCI is significantly less computationally expensive than CD-LMRSDCI on the molecules tested, suggesting that DF-LMRSDCI is an efficient, often sufficiently accurate alternative to our previously reported CD-LMRSDCI method.

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U2 - 10.1021/acs.jctc.5b00762

DO - 10.1021/acs.jctc.5b00762

M3 - Article

C2 - 26574318

AN - SCOPUS:84946944449

VL - 11

SP - 5242

EP - 5251

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

SN - 1549-9618

IS - 11

ER -