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Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

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Published on: April 8, 2020

Two- and four-component relativistic generalized-active-space coupled cluster method: implementation and application

Lasse K Sørensen¹, Jeppe Olsen, Timo Fleig

¹Department of Theoretical Chemistry, Building 26.32, Heinrich Heine University Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany. lks@chem.au.dk

The Journal of Chemical Physics

|June 14, 2011

Summary

A new relativistic coupled-cluster method handles complex electronic structures. This computational chemistry approach accurately models molecules like bismuth monohydride, including outer core electron correlations.

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Area of Science:

Quantum Chemistry
Computational Physics
Relativistic Quantum Mechanics

Background:

Coupled-cluster (CC) methods are essential for accurate electronic structure calculations.
Treating relativistic effects is crucial for heavy elements.
Multi-reference problems often require specialized computational approaches.

Purpose of the Study:

To present a novel string-based coupled-cluster (CC) method incorporating four-component relativistic effects.
To enable the treatment of multi-reference problems using a single-reference framework.
To demonstrate the method's capability in accurately calculating molecular electronic ground states.

Main Methods:

A string-based coupled-cluster (CC) approach with general excitation rank and optimal scaling.
Incorporation of special relativity within a four-component framework.
State-selective expansion of the model space inspired by active-space concepts.
Evaluation of the CC vector function via contractions of second-quantized operators without explicit amplitude equations.

Main Results:

The method was applied to the electronic ground state of bismuth monohydride (BiH).
Simulated multi-reference expansions (up to quadruples excitations) were compared with the standard CC hierarchy.
The significance of atomic outer core-electron correlation for accurate results was highlighted.
Comparisons with the non-relativistic framework illustrated the computational demands of the relativistic approach.

Conclusions:

The developed relativistic CC method effectively handles complex electronic structure problems.
Accurate calculations for heavy-element molecules like BiH require considering outer core-electron correlation.
The four-component relativistic framework presents implementation and application challenges but yields crucial insights.