The 1A1(ππ*) ← X1A1 transition in jet-cooled 4H-pyran-4-thione: Evidence for a dark 1B1(nπ*2) state below 1A1(ππ*)

A. A. Ruth; W. G. Doherty; R. P. Brint

doi:10.1016/S0009-2614(01)01430-0

The ¹A₁(ππ) ← X¹A₁ transition in jet-cooled 4H-pyran-4-thione: Evidence for a dark ¹B₁(nπ₂) state below ¹A₁(ππ*)

A. A. Ruth
, W. G. Doherty
, R. P. Brint

School of Physics

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

Abstract

The ³A₂(nπ*) → X¹A₁ phosphorescence excitation spectrum of jet-cooled 4H-pyran-4-thione (PT) was investigated in the region of the ¹A₁(ππ*) ← X¹A₁ absorption band between 27 300 and 28 800 cm^-1. The spectrum exhibits complex features, which are typical for the (strong) vibronic coupling case of two adjacent electronic states. The observed intermediate level structure was attributed to the coupling with a lower lying dark electronic state ¹B₁(nπ₂*), whose origin was estimated to be ∼825-1025 cm^-1 below the origin ¹A₁(ππ*)₀, using calculations of vibronic state densities in combination with symmetry considerations. Consequences of the vibronic coupling on the decay dynamics of ¹A₁(ππ*) as well as tentative assignments of vibronic transitions ¹A₁(ππ*)_v ← X¹A₁ are also briefly discussed.

Original language	English
Pages (from-to)	191-201
Number of pages	11
Journal	Chemical Physics Letters
Volume	352
Issue number	3-4
DOIs	https://doi.org/10.1016/S0009-2614(01)01430-0
Publication status	Published - 30 Jan 2002

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@article{e0db50e47c0a45ce981eb808ece87684,

title = "The 1A1(ππ*) ← X1A1 transition in jet-cooled 4H-pyran-4-thione: Evidence for a dark 1B1(nπ*2) state below 1A1(ππ*)",

abstract = "The 3A2(nπ*) → X1A1 phosphorescence excitation spectrum of jet-cooled 4H-pyran-4-thione (PT) was investigated in the region of the 1A1(ππ*) ← X1A1 absorption band between 27 300 and 28 800 cm-1. The spectrum exhibits complex features, which are typical for the (strong) vibronic coupling case of two adjacent electronic states. The observed intermediate level structure was attributed to the coupling with a lower lying dark electronic state 1B1(nπ2*), whose origin was estimated to be ∼825-1025 cm-1 below the origin 1A1(ππ*)0, using calculations of vibronic state densities in combination with symmetry considerations. Consequences of the vibronic coupling on the decay dynamics of 1A1(ππ*) as well as tentative assignments of vibronic transitions 1A1(ππ*)v ← X1A1 are also briefly discussed.",

author = "Ruth, \{A. A.\} and Doherty, \{W. G.\} and Brint, \{R. P.\}",

year = "2002",

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doi = "10.1016/S0009-2614(01)01430-0",

language = "English",

volume = "352",

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journal = "Chemical Physics Letters",

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TY - JOUR

T1 - The 1A1(ππ*) ← X1A1 transition in jet-cooled 4H-pyran-4-thione

T2 - Evidence for a dark 1B1(nπ*2) state below 1A1(ππ*)

AU - Ruth, A. A.

AU - Doherty, W. G.

AU - Brint, R. P.

PY - 2002/1/30

Y1 - 2002/1/30

N2 - The 3A2(nπ*) → X1A1 phosphorescence excitation spectrum of jet-cooled 4H-pyran-4-thione (PT) was investigated in the region of the 1A1(ππ*) ← X1A1 absorption band between 27 300 and 28 800 cm-1. The spectrum exhibits complex features, which are typical for the (strong) vibronic coupling case of two adjacent electronic states. The observed intermediate level structure was attributed to the coupling with a lower lying dark electronic state 1B1(nπ2*), whose origin was estimated to be ∼825-1025 cm-1 below the origin 1A1(ππ*)0, using calculations of vibronic state densities in combination with symmetry considerations. Consequences of the vibronic coupling on the decay dynamics of 1A1(ππ*) as well as tentative assignments of vibronic transitions 1A1(ππ*)v ← X1A1 are also briefly discussed.

AB - The 3A2(nπ*) → X1A1 phosphorescence excitation spectrum of jet-cooled 4H-pyran-4-thione (PT) was investigated in the region of the 1A1(ππ*) ← X1A1 absorption band between 27 300 and 28 800 cm-1. The spectrum exhibits complex features, which are typical for the (strong) vibronic coupling case of two adjacent electronic states. The observed intermediate level structure was attributed to the coupling with a lower lying dark electronic state 1B1(nπ2*), whose origin was estimated to be ∼825-1025 cm-1 below the origin 1A1(ππ*)0, using calculations of vibronic state densities in combination with symmetry considerations. Consequences of the vibronic coupling on the decay dynamics of 1A1(ππ*) as well as tentative assignments of vibronic transitions 1A1(ππ*)v ← X1A1 are also briefly discussed.

UR - https://www.scopus.com/pages/publications/0037196527

U2 - 10.1016/S0009-2614(01)01430-0

DO - 10.1016/S0009-2614(01)01430-0

M3 - Article

AN - SCOPUS:0037196527

SN - 0009-2614

VL - 352

SP - 191

EP - 201

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 3-4

ER -

The ¹A₁(ππ) ← X¹A₁ transition in jet-cooled 4H-pyran-4-thione: Evidence for a dark ¹B₁(nπ₂) state below ¹A₁(ππ*)

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