Occurrence and Impact of Electric-Field-Induced Discontinuities in Correlation Energies from Localized Pair-Natural-Orbital Methods
Jose P. Madriaga, T. Daniel Crawford
TL;DR
This paper investigates how electric fields cause small but significant errors in energy calculations using a specific quantum chemistry method.
Contribution
The study reveals that electric-field-induced discontinuities in correlation energies can lead to large errors in computed molecular properties.
Findings
Discontinuities in correlation energy under electric fields can cause over 100% discrepancies in hyperpolarizability calculations.
Weak electric fields can magnify errors due to small field-displacement denominators.
Diffuse basis sets and fixed PNO dimensions do not resolve the issue and may worsen the errors.
Abstract
We report an investigation of discontinuities in the correlation energy produced by external static electric fields within the local pair-natural-orbital coupled-cluster singles and doubles (LPNO-CCSD) method. Such discontinuities arise as a result of variations in both the dimensions and character of the pairwise virtual-orbital domains resulting from changes in the strength of the field. Using several small-molecule test cases – water, fluoroethylene, hypofluorous acid and cis-1,3-butadiene we observe that, although the discontinuities in the correlation energy are small (typically 1 μE h ), they can yield substantial errors in higher-order electric-field-dependent properties computed using finite-difference techniques. For the static hyperpolarizability (third derivative of the energy with respect to the field) of water, for example, the discrepancies between LPNO-CCSD and…
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Taxonomy
TopicsSpectroscopy and Quantum Chemical Studies · Electrochemical Analysis and Applications · thermodynamics and calorimetric analyses