A matrix isolation ESR investigation of Mg + -N 2

Research output: Contribution to journalArticle

Abstract

The adducts formed between 25 Mg + with 14 N 2 and 25 Mg + with 15 N 2 have been trapped in a solid neon matrix and studied with electron spin resonance (ESR) spectroscopy. These radical species were formed through the interaction of laser ablated magnesium and nitrogen gas. The Mg + -N 2 radical species was found to have a ground electronic state of 2 ς + in a linear configuration with discrete coupling to the proximate nitrogen resolved in the spectra. Fitting the ESR spectra allowed magnetic parameters to be determined as follows: g = 2.0012(5), g = 2.0015(8), A (1- 14 N) = 32(3) MHz, A (1- 14 N) = 34(5) MHz, A (1- 15 N) = 45(4) MHz, A (1- 15 N) = 47(6) MHz, A ( 25 Mg) = -581(5) MHz, and A ( 25 Mg) = -582(5) MHz, and estimates derived for A (2- 14 N) = 1(2) MHz, A (2- 14 N) = 2(5) MHz, A (2- 15 N) = 2(2) MHz, and A (2- 15 N) = 4(6) MHz. Ab initio calculations using the coupled-cluster single double triple methodology showed that the linear form was 59.7 kcal mol -1 more stable than the T-shaped form. The potential energy curve around the equilibrium geometry was explored using the complete active space self-consistent field approach, and Hartree-Fock singles and double configuration interaction and multireference singles and double configuration interaction calculations of the hyperfine coupling constants were undertaken, and reasonable agreement with the experiment was observed.

Original languageEnglish
Article number184310
JournalJournal of Chemical Physics
Volume150
Issue number18
DOIs
Publication statusPublished - 14 May 2019

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configuration interaction
Paramagnetic resonance
isolation
electron paramagnetic resonance
Nitrogen
Neon
Electron spin resonance spectroscopy
nitrogen
Electronic states
matrices
Potential energy
neon
Magnesium
adducts
self consistent fields
magnesium
Gases
potential energy
methodology
Geometry

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@article{c3a38a085f8c444992707beb6c036697,
title = "A matrix isolation ESR investigation of Mg + -N 2",
abstract = "The adducts formed between 25 Mg + with 14 N 2 and 25 Mg + with 15 N 2 have been trapped in a solid neon matrix and studied with electron spin resonance (ESR) spectroscopy. These radical species were formed through the interaction of laser ablated magnesium and nitrogen gas. The Mg + -N 2 radical species was found to have a ground electronic state of 2 ς + in a linear configuration with discrete coupling to the proximate nitrogen resolved in the spectra. Fitting the ESR spectra allowed magnetic parameters to be determined as follows: g ∥ = 2.0012(5), g ⊥ = 2.0015(8), A ∥ (1- 14 N) = 32(3) MHz, A ⊥ (1- 14 N) = 34(5) MHz, A ∥ (1- 15 N) = 45(4) MHz, A ⊥ (1- 15 N) = 47(6) MHz, A ∥ ( 25 Mg) = -581(5) MHz, and A ⊥ ( 25 Mg) = -582(5) MHz, and estimates derived for A ∥ (2- 14 N) = 1(2) MHz, A ⊥ (2- 14 N) = 2(5) MHz, A ∥ (2- 15 N) = 2(2) MHz, and A ⊥ (2- 15 N) = 4(6) MHz. Ab initio calculations using the coupled-cluster single double triple methodology showed that the linear form was 59.7 kcal mol -1 more stable than the T-shaped form. The potential energy curve around the equilibrium geometry was explored using the complete active space self-consistent field approach, and Hartree-Fock singles and double configuration interaction and multireference singles and double configuration interaction calculations of the hyperfine coupling constants were undertaken, and reasonable agreement with the experiment was observed.",
author = "Hearne, {Thomas S.} and Wild, {Duncan A.} and McKinley, {Allan J.}",
year = "2019",
month = "5",
day = "14",
doi = "10.1063/1.5090923",
language = "English",
volume = "150",
journal = "The Journal of Chemical Physics",
issn = "0021-9606",
publisher = "ACOUSTICAL SOC AMER AMER INST PHYSICS",
number = "18",

}

A matrix isolation ESR investigation of Mg + -N 2. / Hearne, Thomas S.; Wild, Duncan A.; McKinley, Allan J.

In: Journal of Chemical Physics, Vol. 150, No. 18, 184310, 14.05.2019.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A matrix isolation ESR investigation of Mg + -N 2

AU - Hearne, Thomas S.

AU - Wild, Duncan A.

AU - McKinley, Allan J.

PY - 2019/5/14

Y1 - 2019/5/14

N2 - The adducts formed between 25 Mg + with 14 N 2 and 25 Mg + with 15 N 2 have been trapped in a solid neon matrix and studied with electron spin resonance (ESR) spectroscopy. These radical species were formed through the interaction of laser ablated magnesium and nitrogen gas. The Mg + -N 2 radical species was found to have a ground electronic state of 2 ς + in a linear configuration with discrete coupling to the proximate nitrogen resolved in the spectra. Fitting the ESR spectra allowed magnetic parameters to be determined as follows: g ∥ = 2.0012(5), g ⊥ = 2.0015(8), A ∥ (1- 14 N) = 32(3) MHz, A ⊥ (1- 14 N) = 34(5) MHz, A ∥ (1- 15 N) = 45(4) MHz, A ⊥ (1- 15 N) = 47(6) MHz, A ∥ ( 25 Mg) = -581(5) MHz, and A ⊥ ( 25 Mg) = -582(5) MHz, and estimates derived for A ∥ (2- 14 N) = 1(2) MHz, A ⊥ (2- 14 N) = 2(5) MHz, A ∥ (2- 15 N) = 2(2) MHz, and A ⊥ (2- 15 N) = 4(6) MHz. Ab initio calculations using the coupled-cluster single double triple methodology showed that the linear form was 59.7 kcal mol -1 more stable than the T-shaped form. The potential energy curve around the equilibrium geometry was explored using the complete active space self-consistent field approach, and Hartree-Fock singles and double configuration interaction and multireference singles and double configuration interaction calculations of the hyperfine coupling constants were undertaken, and reasonable agreement with the experiment was observed.

AB - The adducts formed between 25 Mg + with 14 N 2 and 25 Mg + with 15 N 2 have been trapped in a solid neon matrix and studied with electron spin resonance (ESR) spectroscopy. These radical species were formed through the interaction of laser ablated magnesium and nitrogen gas. The Mg + -N 2 radical species was found to have a ground electronic state of 2 ς + in a linear configuration with discrete coupling to the proximate nitrogen resolved in the spectra. Fitting the ESR spectra allowed magnetic parameters to be determined as follows: g ∥ = 2.0012(5), g ⊥ = 2.0015(8), A ∥ (1- 14 N) = 32(3) MHz, A ⊥ (1- 14 N) = 34(5) MHz, A ∥ (1- 15 N) = 45(4) MHz, A ⊥ (1- 15 N) = 47(6) MHz, A ∥ ( 25 Mg) = -581(5) MHz, and A ⊥ ( 25 Mg) = -582(5) MHz, and estimates derived for A ∥ (2- 14 N) = 1(2) MHz, A ⊥ (2- 14 N) = 2(5) MHz, A ∥ (2- 15 N) = 2(2) MHz, and A ⊥ (2- 15 N) = 4(6) MHz. Ab initio calculations using the coupled-cluster single double triple methodology showed that the linear form was 59.7 kcal mol -1 more stable than the T-shaped form. The potential energy curve around the equilibrium geometry was explored using the complete active space self-consistent field approach, and Hartree-Fock singles and double configuration interaction and multireference singles and double configuration interaction calculations of the hyperfine coupling constants were undertaken, and reasonable agreement with the experiment was observed.

UR - http://www.scopus.com/inward/record.url?scp=85065738957&partnerID=8YFLogxK

U2 - 10.1063/1.5090923

DO - 10.1063/1.5090923

M3 - Article

VL - 150

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

SN - 0021-9606

IS - 18

M1 - 184310

ER -