A Benchmark Study of Aromaticity Indexes for Benzene, Pyridine, and the Diazines-II. Excited State Aromaticity

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A Benchmark Study of Aromaticity Indexes for Benzene, Pyridine, and the Diazines-II. Excited State Aromaticity. / Pedersen, Jacob; Mikkelsen, Kurt V.

I: Journal of Physical Chemistry A, Bind 127, Nr. 1, 2023, s. 122–130.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt

Harvard

Pedersen, J & Mikkelsen, KV 2023, 'A Benchmark Study of Aromaticity Indexes for Benzene, Pyridine, and the Diazines-II. Excited State Aromaticity', Journal of Physical Chemistry A, bind 127, nr. 1, s. 122–130. https://doi.org/10.1021/acs.jpca.2c07059

APA

Pedersen, J., & Mikkelsen, K. V. (2023). A Benchmark Study of Aromaticity Indexes for Benzene, Pyridine, and the Diazines-II. Excited State Aromaticity. Journal of Physical Chemistry A, 127(1), 122–130. https://doi.org/10.1021/acs.jpca.2c07059

Vancouver

Pedersen J, Mikkelsen KV. A Benchmark Study of Aromaticity Indexes for Benzene, Pyridine, and the Diazines-II. Excited State Aromaticity. Journal of Physical Chemistry A. 2023;127(1):122–130. https://doi.org/10.1021/acs.jpca.2c07059

Author

Pedersen, Jacob ; Mikkelsen, Kurt V. / A Benchmark Study of Aromaticity Indexes for Benzene, Pyridine, and the Diazines-II. Excited State Aromaticity. I: Journal of Physical Chemistry A. 2023 ; Bind 127, Nr. 1. s. 122–130.

Bibtex

@article{66ceb2b09ed6403f91483fb2ed994582,
title = "A Benchmark Study of Aromaticity Indexes for Benzene, Pyridine, and the Diazines-II. Excited State Aromaticity",
abstract = "In this work, one geometrical aromaticity index and four electron sharing indexes are benchmarked for their application in excited state aromaticity calculations. Two computationally feasible and reliable procedures are identified, namely, CAM-B3LYP/cc-pVTZ and omega B97X-D/cc-pVTZ. Topological effects on the first excited singlet and triplet electronic manifold were investigated, and the latter was in general found to display more aromatic character compared to the S1 surface. Besides, geometrical relaxation on each of the manifolds was observed to hamper the aromaticity, thereby resulting in more antiaromatic character. The relative order of excited state aromaticity within the studied molecules was noted to resemble the reversed version of the relative order of ground state aromaticity. Thereby, the following generalization was postulated: The more aromatic a molecule is in its ground state, the more antiaromatic it will be in its electronic first excited manifolds.",
keywords = "DENSITY-FUNCTIONAL THEORY, GAUSSIAN-BASIS SETS, CORRELATED MOLECULAR CALCULATIONS, QUADRATIC RESPONSE FUNCTIONS, ELECTRON DELOCALIZATION, ORGANIC-PHOTOCHEMISTRY, ORBITAL METHODS, GROUND-STATE, ATOMS, ANTIAROMATICITY",
author = "Jacob Pedersen and Mikkelsen, {Kurt V.}",
year = "2023",
doi = "10.1021/acs.jpca.2c07059",
language = "English",
volume = "127",
pages = "122–130",
journal = "Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "1",

}

RIS

TY - JOUR

T1 - A Benchmark Study of Aromaticity Indexes for Benzene, Pyridine, and the Diazines-II. Excited State Aromaticity

AU - Pedersen, Jacob

AU - Mikkelsen, Kurt V.

PY - 2023

Y1 - 2023

N2 - In this work, one geometrical aromaticity index and four electron sharing indexes are benchmarked for their application in excited state aromaticity calculations. Two computationally feasible and reliable procedures are identified, namely, CAM-B3LYP/cc-pVTZ and omega B97X-D/cc-pVTZ. Topological effects on the first excited singlet and triplet electronic manifold were investigated, and the latter was in general found to display more aromatic character compared to the S1 surface. Besides, geometrical relaxation on each of the manifolds was observed to hamper the aromaticity, thereby resulting in more antiaromatic character. The relative order of excited state aromaticity within the studied molecules was noted to resemble the reversed version of the relative order of ground state aromaticity. Thereby, the following generalization was postulated: The more aromatic a molecule is in its ground state, the more antiaromatic it will be in its electronic first excited manifolds.

AB - In this work, one geometrical aromaticity index and four electron sharing indexes are benchmarked for their application in excited state aromaticity calculations. Two computationally feasible and reliable procedures are identified, namely, CAM-B3LYP/cc-pVTZ and omega B97X-D/cc-pVTZ. Topological effects on the first excited singlet and triplet electronic manifold were investigated, and the latter was in general found to display more aromatic character compared to the S1 surface. Besides, geometrical relaxation on each of the manifolds was observed to hamper the aromaticity, thereby resulting in more antiaromatic character. The relative order of excited state aromaticity within the studied molecules was noted to resemble the reversed version of the relative order of ground state aromaticity. Thereby, the following generalization was postulated: The more aromatic a molecule is in its ground state, the more antiaromatic it will be in its electronic first excited manifolds.

KW - DENSITY-FUNCTIONAL THEORY

KW - GAUSSIAN-BASIS SETS

KW - CORRELATED MOLECULAR CALCULATIONS

KW - QUADRATIC RESPONSE FUNCTIONS

KW - ELECTRON DELOCALIZATION

KW - ORGANIC-PHOTOCHEMISTRY

KW - ORBITAL METHODS

KW - GROUND-STATE

KW - ATOMS

KW - ANTIAROMATICITY

U2 - 10.1021/acs.jpca.2c07059

DO - 10.1021/acs.jpca.2c07059

M3 - Journal article

C2 - 36548541

VL - 127

SP - 122

EP - 130

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

SN - 1089-5639

IS - 1

ER -

ID: 332036179