Chlorocyclohexane valence and Rydberg electronic excitations

E. Bandeira; Sarvesh Kumar; Nykola C. Jones; Søren Vrønning Hoffmann; Marcio H. F. Bettega; Paulo Limao-Vieira

doi:10.1021/acs.jpca.5c01122

Chlorocyclohexane valence and Rydberg electronic excitations

E. Bandeira, Sarvesh Kumar, Nykola C. Jones, Søren Vrønning Hoffmann, Marcio H. F. Bettega, Paulo Limao-Vieira

Department of Physics and Astronomy - Centre for Storage Ring Facilities (ISA)

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

Abstract

Here we present new cross-section values of chlorocyclohexane (C₆H₁₁Cl) from vacuum ultraviolet (VUV) photoabsorption measurements in the photon energy range of 5.0-10.8 eV (115-248 nm). Theoretical calculations using time-dependent density functional theory (TD-DFT) have been performed to aid in the interpretation of the photoabsorption spectrum. The information from these calculations has allowed the assignment of the excited states in valence, mixed valence-Rydberg, and Rydberg transitions. The fine features in the photoabsorption bands have been assigned to (C-H₂)₄ symmetric stretching (and C-H stretching), (Formula presented), (C-H₂)₄ wagging, (Formula presented) and ring puckering/C-Cl stretching (Formula presented) modes. From the absolute cross-section values, photolysis lifetimes in the Earth’s atmosphere have been estimated, showing that solar photolysis may only be considered a relevant sink at altitudes above 20 km. Additional calculations at the TD-DFT level of theory have been performed to obtain potential energy curves for the lowest-lying electronic states, highlighting the role of predissociative character.

Original language	English
Journal	The Journal of Physical Chemistry Part A
Volume	129
Issue	17
Pages (from-to)	3857-3866
Number of pages	10
ISSN	1089-5639
DOIs	https://doi.org/10.1021/acs.jpca.5c01122
Publication status	Published - 2025

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@article{fdce6047c4b0498e8a1dd390960143b1,

title = "Chlorocyclohexane valence and Rydberg electronic excitations",

abstract = "Here we present new cross-section values of chlorocyclohexane (C6H11Cl) from vacuum ultraviolet (VUV) photoabsorption measurements in the photon energy range of 5.0-10.8 eV (115-248 nm). Theoretical calculations using time-dependent density functional theory (TD-DFT) have been performed to aid in the interpretation of the photoabsorption spectrum. The information from these calculations has allowed the assignment of the excited states in valence, mixed valence-Rydberg, and Rydberg transitions. The fine features in the photoabsorption bands have been assigned to (C-H2)4 symmetric stretching (and C-H stretching), (Formula presented), (C-H2)4 wagging, (Formula presented) and ring puckering/C-Cl stretching (Formula presented) modes. From the absolute cross-section values, photolysis lifetimes in the Earth{\textquoteright}s atmosphere have been estimated, showing that solar photolysis may only be considered a relevant sink at altitudes above 20 km. Additional calculations at the TD-DFT level of theory have been performed to obtain potential energy curves for the lowest-lying electronic states, highlighting the role of predissociative character.",

author = "E. Bandeira and Sarvesh Kumar and Jones, {Nykola C.} and Hoffmann, {S{\o}ren Vr{\o}nning} and Bettega, {Marcio H. F.} and Paulo Limao-Vieira",

year = "2025",

doi = "10.1021/acs.jpca.5c01122",

language = "English",

volume = "129",

pages = "3857--3866",

journal = "The Journal of Physical Chemistry Part A",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "17",

}

TY - JOUR

T1 - Chlorocyclohexane valence and Rydberg electronic excitations

AU - Bandeira, E.

AU - Kumar, Sarvesh

AU - Jones, Nykola C.

AU - Hoffmann, Søren Vrønning

AU - Bettega, Marcio H. F.

AU - Limao-Vieira, Paulo

PY - 2025

Y1 - 2025

N2 - Here we present new cross-section values of chlorocyclohexane (C6H11Cl) from vacuum ultraviolet (VUV) photoabsorption measurements in the photon energy range of 5.0-10.8 eV (115-248 nm). Theoretical calculations using time-dependent density functional theory (TD-DFT) have been performed to aid in the interpretation of the photoabsorption spectrum. The information from these calculations has allowed the assignment of the excited states in valence, mixed valence-Rydberg, and Rydberg transitions. The fine features in the photoabsorption bands have been assigned to (C-H2)4 symmetric stretching (and C-H stretching), (Formula presented), (C-H2)4 wagging, (Formula presented) and ring puckering/C-Cl stretching (Formula presented) modes. From the absolute cross-section values, photolysis lifetimes in the Earth’s atmosphere have been estimated, showing that solar photolysis may only be considered a relevant sink at altitudes above 20 km. Additional calculations at the TD-DFT level of theory have been performed to obtain potential energy curves for the lowest-lying electronic states, highlighting the role of predissociative character.

AB - Here we present new cross-section values of chlorocyclohexane (C6H11Cl) from vacuum ultraviolet (VUV) photoabsorption measurements in the photon energy range of 5.0-10.8 eV (115-248 nm). Theoretical calculations using time-dependent density functional theory (TD-DFT) have been performed to aid in the interpretation of the photoabsorption spectrum. The information from these calculations has allowed the assignment of the excited states in valence, mixed valence-Rydberg, and Rydberg transitions. The fine features in the photoabsorption bands have been assigned to (C-H2)4 symmetric stretching (and C-H stretching), (Formula presented), (C-H2)4 wagging, (Formula presented) and ring puckering/C-Cl stretching (Formula presented) modes. From the absolute cross-section values, photolysis lifetimes in the Earth’s atmosphere have been estimated, showing that solar photolysis may only be considered a relevant sink at altitudes above 20 km. Additional calculations at the TD-DFT level of theory have been performed to obtain potential energy curves for the lowest-lying electronic states, highlighting the role of predissociative character.

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U2 - 10.1021/acs.jpca.5c01122

DO - 10.1021/acs.jpca.5c01122

M3 - Journal article

SN - 1089-5639

VL - 129

SP - 3857

EP - 3866

JO - The Journal of Physical Chemistry Part A

JF - The Journal of Physical Chemistry Part A

IS - 17

ER -

Chlorocyclohexane valence and Rydberg electronic excitations

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