Density matrices in full configuration interaction quantum Monte Carlo: Excited states, transition dipole moments, and parallel distribution

N. S. Blunt; George H. Booth; Ali Alavi

doi:10.1063/1.4986963

Density matrices in full configuration interaction quantum Monte Carlo: Excited states, transition dipole moments, and parallel distribution

N. S. Blunt, George H. Booth, Ali Alavi

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Abstract

We present developments in the calculation of reduced density matrices (RDMs) in the full configuration interaction quantum Monte Carlo (FCIQMC) method. An efficient scheme is described to allow storage of RDMs across distributed memory, thereby allowing their calculation and storage in large basis sets. We demonstrate the calculation of RDMs for general states by using the recently introduced excited-state FCIQMC approach [N. S. Blunt et al., J. Chem. Phys. 143, 134117 (2015)] and further introduce calculation of transition density matrices in the method. These approaches are combined to calculate excited-state dipole and transition dipole moments for heteronuclear diatomic molecules, including LiH, BH, and MgO, and initiator error is investigated in these quantities.

Original language	English
Article number	244105
Journal	Journal of Chemical Physics
Volume	146
Issue number	24
DOIs	https://doi.org/10.1063/1.4986963
Publication status	Published - 26 Jun 2017

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Density matrices in full_BLUNT_Accepted7June2017_GREEN AAM (non-CC)
Published in The Journal of Chemical Physics 146, 244105 (2017); doi: http://dx.doi.org/10.1063/1.4986963. Published by AIP Publishing.
Accepted author manuscript, 317 KBLicence: Other
Density matrices in full_BLUNT_Accepted7June2017_GREEN VoRFinal published version, 602 KB

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title = "Density matrices in full configuration interaction quantum Monte Carlo: Excited states, transition dipole moments, and parallel distribution",

abstract = "We present developments in the calculation of reduced density matrices (RDMs) in the full configuration interaction quantum Monte Carlo (FCIQMC) method. An efficient scheme is described to allow storage of RDMs across distributed memory, thereby allowing their calculation and storage in large basis sets. We demonstrate the calculation of RDMs for general states by using the recently introduced excited-state FCIQMC approach [N. S. Blunt et al., J. Chem. Phys. 143, 134117 (2015)] and further introduce calculation of transition density matrices in the method. These approaches are combined to calculate excited-state dipole and transition dipole moments for heteronuclear diatomic molecules, including LiH, BH, and MgO, and initiator error is investigated in these quantities.",

author = "Blunt, {N. S.} and Booth, {George H.} and Ali Alavi",

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T1 - Density matrices in full configuration interaction quantum Monte Carlo

T2 - Excited states, transition dipole moments, and parallel distribution

AU - Blunt, N. S.

AU - Booth, George H.

AU - Alavi, Ali

PY - 2017/6/26

Y1 - 2017/6/26

N2 - We present developments in the calculation of reduced density matrices (RDMs) in the full configuration interaction quantum Monte Carlo (FCIQMC) method. An efficient scheme is described to allow storage of RDMs across distributed memory, thereby allowing their calculation and storage in large basis sets. We demonstrate the calculation of RDMs for general states by using the recently introduced excited-state FCIQMC approach [N. S. Blunt et al., J. Chem. Phys. 143, 134117 (2015)] and further introduce calculation of transition density matrices in the method. These approaches are combined to calculate excited-state dipole and transition dipole moments for heteronuclear diatomic molecules, including LiH, BH, and MgO, and initiator error is investigated in these quantities.

AB - We present developments in the calculation of reduced density matrices (RDMs) in the full configuration interaction quantum Monte Carlo (FCIQMC) method. An efficient scheme is described to allow storage of RDMs across distributed memory, thereby allowing their calculation and storage in large basis sets. We demonstrate the calculation of RDMs for general states by using the recently introduced excited-state FCIQMC approach [N. S. Blunt et al., J. Chem. Phys. 143, 134117 (2015)] and further introduce calculation of transition density matrices in the method. These approaches are combined to calculate excited-state dipole and transition dipole moments for heteronuclear diatomic molecules, including LiH, BH, and MgO, and initiator error is investigated in these quantities.

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M3 - Article

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VL - 146

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 24

M1 - 244105

ER -

Density matrices in full configuration interaction quantum Monte Carlo: Excited states, transition dipole moments, and parallel distribution

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