Toluene Valence and Rydberg Excitations as Studied by ab initio Calculations and Vacuum Ultraviolet (VUV) Synchrotron Radiation

被引：19

作者：

Serralheiro, C. ^{[1
,2
]}

Duflot, D. ^{[3
]}

da Silva, F. Ferreira ^{[1
]}

Hoffmann, S. V. ^{[4
]}

Jones, N. C. ^{[4
]}

Mason, N. J. ^{[5
]}

Mendes, B. ^{[2
]}

Limao-Vieira, P. ^{[1
,5
]}

机构：

[1] Univ Nova Lisboa, Dept Fis, Lab Colisoes Atom & Mol, CEFITEC,Fac Ciencias & Tecnol, P-2829516 Caparica, Portugal

[2] Univ Nova Lisboa, Fac Ciencias & Tecnol, Dept Ciencias & Tecnol Biomassa, Ctr Engn Mecan & Sustentabilidade Recursos MEtRIC, P-2829516 Caparica, Portugal

[3] Univ Lille, Lab Phys Lasers Atomes & Mol PhLAM, CNRS, UMR 8523, F-59655 Villeneuve Dascq, France

[4] Aarhus Univ, Dept Phys & Astron, ISA, DK-8000 Aarhus C, Denmark

[5] Open Univ, Dept Phys Sci, Milton Keynes MK7 6AA, Bucks, England

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2015年 / 119卷 / 34期

关键词：

ABSORPTION CROSS-SECTIONS; GAUSSIAN-BASIS SETS; EXCITED-STATE; SPECTROSCOPY; UV; BENZENE; SPECTRA; PHOTOABSORPTION; TRANSITION; OXIDATION;

D O I：

10.1021/acs.jpca.5b05080

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The electronic spectroscopy of isolated toluene in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 4.0-10.8 eV energy range, with absolute cross-section measurements derived. We present the first set of ab initio calculations (vertical energies and oscillator strengths), which we use in the assignment of valence and Rydberg transitions of the toluene molecule. The spectrum reveals several new features not previously reported in the literature, with particular relevance to 7.989 and 8.958 eV, which are here tentatively assigned to the pi*(17a' <- sigma(15a') and 1 pi*(10a") <- 1 pi(14a') transitions, respectively. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of toluene in the upper stratosphere (20-50 km).

引用

页码：9059 / 9069

页数：11

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