Efficient Computation of Two-Electron Reduced Density Matrices via Selected Configuration Interaction

被引：11

作者：

Coe, Jeremy P. ^{[1
]}

Carrascosa, Andres Moreno ^{[2
,3
]}

Simmermacher, Mats ^{[2
,3
]}

Kirrander, Adam ^{[2
,3
]}

Paterson, Martin J. ^{[1
]}

机构：

[1] Heriot Watt Univ, Inst Chem Sci, Sch Engn & Phys Sci, Edinburgh EH14 4AS, Midlothian, Scotland

[2] Univ Edinburgh, Sch Chem, EaStCHEM, Edinburgh EH9 3FJ, Midlothian, Scotland

[3] Univ Oxford, Dept Chem, Phys & Theoret Chem Lab, South Parks Rd, Oxford OX1 3QZ, England

来源：

JOURNAL OF CHEMICAL THEORY AND COMPUTATION | 2022年

基金：

英国工程与自然科学研究理事会;

关键词：

AB-INITIO CALCULATION; ENERGIES;

D O I：

10.1021/acs.jctc.2c00738

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We create an approach to efficiently calculate two-electron reduced density matrices (2-RDMs) using selected configuration interaction wavefunctions. This is demonstrated using the specific example of Monte Carlo configuration interaction (MCCI). The computation of the 2-RDMs is accelerated by using ideas from fast implementations of full configuration interaction (FCI) and recent advances in implementing the Slater-Condon rules using hardware bitwise operations. This method enables a comparison of MCCI and truncated CI 2-RDMs with FCI values for a range of molecules, which includes stretched bonds and excited states. The accuracy in energies, wavefunctions, and 2-RDMs is seen to exhibit a similar behavior. We find that MCCI can reach sufficient accuracy of the 2-RDM using significantly fewer configurations than truncated CI, particularly for systems with strong multireference character.

引用

页码：6690 / 6699

页数：10

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