Sensitivity of Photoelectron Angular Distributions to Molecular Conformations of Anions

Cate S Anstöter; Charlie R Dean; Jan R R Verlet

doi:10.1021/acs.jpclett.7b00726

Sensitivity of Photoelectron Angular Distributions to Molecular Conformations of Anions

Cate S Anstöter, Charlie R Dean, Jan R R Verlet

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

An anion photoelectron imaging study probing the sensitivity of the photoelectron angular distribution (PAD) to conformational changes is presented. The PADs of a series of para-substituted phenolate anions is compared with those calculated using the Dyson orbital formalization. Good agreement was attained for the two observed direct detachment channels of all anions, except for the lowest-energy detachment channel of para-ethyl phenolate for which two conformations exist that yield very different PADs. The conformational freedom leads to an observed PAD that is the incoherent sum of the PADs from all conformers populated under experimental conditions. In contrast, a second detachment channel shows no sensitivity to the conformational flexibility of para-ethyl phenolate. Our results show that PADs can provide detailed information about the electronic structure of the anion and its conformations.

Original language	English
Pages (from-to)	2268-2273
Number of pages	6
Journal	JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume	8
Issue number	10
Early online date	8 May 2017
DOIs	https://doi.org/10.1021/acs.jpclett.7b00726
Publication status	Published - 18 May 2017

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10.1021/acs.jpclett.7b00726

Cite this

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title = "Sensitivity of Photoelectron Angular Distributions to Molecular Conformations of Anions",

abstract = "An anion photoelectron imaging study probing the sensitivity of the photoelectron angular distribution (PAD) to conformational changes is presented. The PADs of a series of para-substituted phenolate anions is compared with those calculated using the Dyson orbital formalization. Good agreement was attained for the two observed direct detachment channels of all anions, except for the lowest-energy detachment channel of para-ethyl phenolate for which two conformations exist that yield very different PADs. The conformational freedom leads to an observed PAD that is the incoherent sum of the PADs from all conformers populated under experimental conditions. In contrast, a second detachment channel shows no sensitivity to the conformational flexibility of para-ethyl phenolate. Our results show that PADs can provide detailed information about the electronic structure of the anion and its conformations.",

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AU - Dean, Charlie R

AU - Verlet, Jan R R

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AB - An anion photoelectron imaging study probing the sensitivity of the photoelectron angular distribution (PAD) to conformational changes is presented. The PADs of a series of para-substituted phenolate anions is compared with those calculated using the Dyson orbital formalization. Good agreement was attained for the two observed direct detachment channels of all anions, except for the lowest-energy detachment channel of para-ethyl phenolate for which two conformations exist that yield very different PADs. The conformational freedom leads to an observed PAD that is the incoherent sum of the PADs from all conformers populated under experimental conditions. In contrast, a second detachment channel shows no sensitivity to the conformational flexibility of para-ethyl phenolate. Our results show that PADs can provide detailed information about the electronic structure of the anion and its conformations.

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