Coupled-cluster Approaches To Electric Polarizabilities For Long-range Force Fields

Coy, Stephen L

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https://hdl.handle.net/2142/111441 Copy

Description

Title

Coupled-cluster Approaches To Electric Polarizabilities For Long-range Force Fields

Author(s)

Coy, Stephen L

Contributor(s)

• Stanton, John F.
• Field, Robert W
• Barnum, Timothy J

Issue Date

2021-06-22

Keyword(s)

Comparing theory and experiment

Abstract

Whether in ionic or covalent bonding, in weakly bound clusters, in liquids, or in solids, perturbed electronic structure contributes to spectroscopy, electromagnetic interactions and enhanced reactivity. For Rydberg states, effects of current interest include vibrational autoionization as discussed by Ed Eyler and by Timothy Barnum The range of importance of classical force fields extends through VdW clusters up to biological problems such as enhanced protein folding from fluorine-substitution in proteins. For smaller molecules and Rydberg ion cores such as NO+ or alkaline earth mono-halide cations, accurate coupled cluster methods are quite feasible at the CCSD(T) or CCSDT level, using augmented basis sets up to the quadruple-zeta level. These methods can be used in the CFOUR ab-initio suite to determine polarizability expansions giving the local force field out to quite high order. Several approaches will be described, including arrays of test-charges, the use of implemented analytical derivatives, and static field perturbations. This presentation will focus on results useful for modeling Rydberg vibrational autoionization in NO Rydberg states.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

Text

Language

eng

Permalink

http://hdl.handle.net/2142/111441

DOI

10.15278/isms.2021.TK12

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