Electronic structure of nitrogen dioxide, its ions, and its dimer

Burnelle, Louis; Beaudouin, P.; Schaad, L. J.

doi:10.1021/j100866a043

Cited by 33 publications

(15 citation statements)

References 8 publications

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“…where H eff is the effective one-electron Hamiltonian. 45,46 Utilizing the Wolfsberg−Helmholtz formula, 45,47,48 the hopping integral can be approximated by the sum of the relevant diagonal elements (H μμ and H νν ) multiplied by the overlap integral (S μν ) such that…”

Section: Resultsmentioning

confidence: 99%

Spectroscopic Probe Molecule Selection Using Quantum Theory, First-Principles Calculations, and Machine Learning

Lansford

Vlachos

2020

ACS Nano

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Probe molecule vibrational spectra have a long history of being used to characterize materials including metals, oxides, metal−organic frameworks, and even human proteins. Furthermore, recent advances in machine learning have enabled computationally generated spectra to aid in detailed characterization of complex surfaces with probe molecules. Despite widespread use of probe molecules, the science of probe molecule selection is underdeveloped. Here, we develop physical concepts, including orbital interaction energy and the energy overlap integral, to explain and predict the ability of probe molecules to discriminate structural descriptors. We resolve the crystal orbital overlap population (COOP) to specific molecular orbitals and quantify their bonding character, which directly influences vibrational frequencies. Using only a single adsorbate calculation from density function theory (DFT), we compute the interaction energy of individual adsorbate molecular orbitals with adsorption site atomic orbitals across many different sites. Combining the molecular orbital resolved COOP and changes in orbital interaction energy enables probe molecule selection for improved discrimination of various sites. We demonstrate these concepts by comparing the predicted effectiveness of carbon monoxide (CO), nitric oxide (NO), and ethylene (C 2 H 4 ) to probe Pt adsorption sites. Finally, using a previously developed machine learning framework, we show that models trained on hundreds of thousands of C 2 H 4 spectra, computed from DFT, which regress surface binding-type and generalized coordination number, outperform those trained using CO and NO spectra. A python package, pDOS_overlap, for implementing the electron density-based analysis on any combination of adsorbates and materials, is also made available.

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Section: Resultsmentioning

confidence: 99%

Spectroscopic Probe Molecule Selection Using Quantum Theory, First-Principles Calculations, and Machine Learning

Lansford

Vlachos

2020

ACS Nano

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“…32,42 It should be noted that it may be possible for additional interaction between these π orbitals, given that the CuPc LUMO and HOMO of NO 2 – are of π character. 42,53…”

Section: Resultsmentioning

confidence: 99%

Interaction of Copper Phthalocyanine with Nitrogen Dioxide and Ammonia Investigation Using X-ray Absorption Spectroscopy and Chemiresistive Gas Measurements

Chia

Suresh³

et al. 2019

ACS Omega

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The interaction site of phthalocyanine (Pc) with nitrogen dioxide (NO 2 ) has been characterized using different methods and found to be conflicting. By knowing the interaction site, the Pc molecule can be better customized to improve the gas sensitivity. In this article, the interaction sites of copper phthalocyanine (CuPc) with oxidizing NO 2 or with reducing gas (ammonia, NH 3 ) were identified using in situ X-ray absorption spectroscopy (XAS). The sensitivity of CuPc to sub-ppm levels of the tested gases was established in the CuPc chemoresistive gas sensors. The analyte–sensor interaction sites were identified and validated by monitoring the Cu K-edge XAS before and during gas exposure. From the X-ray absorption near-edge structure and its first derivative, a low or lack of axial coordination on the Cu metal center of CuPc is evident. Using the extended X-ray absorption fine structure with molecular orbital information of the involved molecules, the macrocycle interaction between CuPc and NO 2 or NH 3 was proposed to be the dominant sensing mechanism on CuPc sensors.

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“…Adduct formation with either surfaces 59 or metal ions 60 breaks the π * degeneracy and leads to observable EPR resonances. 79 The resulting unpaired electron is largely localized on the nitrogen but there are many low lying excited states and configuration interaction with these is required for a complete description of the electronic structure. 40,74 -76 Low lying excited states for nitric oxide include a Rydberg σ 2 σ 2 lp σ 2 lp π 4 π * 0 σ 1 ryd A 2 state from the excitation of an electron to an s-type Rydberg orbital, and two, 4 and B 2 states, which arise from a π → π * excitation and correspond to π 3 π * 2 configurations.…”

Section: Electronic Structure Of Nitrogen Oxidesmentioning

confidence: 99%

The Nitrogen Oxides: Persistent Radicals and van der Waals Complex Dimers

Bohle¹

2010

Stable Radicals

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Electronic structure of nitrogen dioxide, its ions, and its dimer

Cited by 33 publications

References 8 publications

Spectroscopic Probe Molecule Selection Using Quantum Theory, First-Principles Calculations, and Machine Learning

Spectroscopic Probe Molecule Selection Using Quantum Theory, First-Principles Calculations, and Machine Learning

Interaction of Copper Phthalocyanine with Nitrogen Dioxide and Ammonia Investigation Using X-ray Absorption Spectroscopy and Chemiresistive Gas Measurements

The Nitrogen Oxides: Persistent Radicals and van der Waals Complex Dimers

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