Solvent and Heavy-Atom Effects on the O2(X3Σg-) → O2(b1Σg+) Absorption Transition

被引:29
作者
Bregnhoj, Mikkel [1 ]
Kraegpoth, Mikkel V. [1 ]
Sorensen, Rasmus Juhl [1 ]
Westberg, Michael [1 ]
Ogilby, Peter R. [1 ]
机构
[1] Aarhus Univ, Dept Chem, DK-8000 Aarhus, Denmark
基金
新加坡国家研究基金会;
关键词
SINGLET-MOLECULAR-OXYGEN; RADIATIVE TRANSITIONS; VARIABLE-TEMPERATURE; AROMATIC KETONES; RATE CONSTANTS; 765; NM; LIFETIMES; REACTIVITY; TRYPTOPHAN; EMISSION;
D O I
10.1021/acs.jpca.6b08035
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 effect of 16 liquid solvents on both the spectrum and molar absorption coefficient of the X-3 Sigma(-)(g) -> b(1)Sigma(+)(g) transition in molecular oxygen has been examined. The ability to monitor this weak transition using air or oxygen saturated samples at atmospheric pressure was facilitated by the rapid and efficient O-2(b(1)Sigma(+)(g)) -> O-2(a(1)Delta(g)) transition, which allowed the use of O-2(a(1)Delta(g)) phosphorescence as a sensitive probe of O-2(b(1)Sigma(+)(g)) production. The results of these O-2(a(1)Delta(g)) phosphorescence experiments are consistent with the results of independent experiments in which the O-2(a(1)Delta(g)) thus produced was "trapped" via a chemical reaction. The data recorded were used to calculate rate constants for the O-2(b(1)Sigma(+)(g)) -> O-2(X-3 Sigma(-)(g)) radiative transition, a parameter that is otherwise difficult to directly obtain from such a wide range of solvents using O-2(b(1)Sigma(+)(g)) -> O-2(X-3 Sigma(-)(g)) phosphorescence. The data show that the response of the O-2(b(1)Sigma(+)(g)) -> O-2(X-3 Sigma(-)(g)) radiative transition to solvent is not the same as that of the O-2(b(1)Sigma(+)(g)) -> O-2(a(1)Delta(g)) and O-2(a(1)Delta(g)) -> O-2(X-3 Sigma(-)(g)) radiative transitions, both of which have been extensively examined over the years. However, our data are consistent with a theoretical model proposed by Minaev for the effect of solvent on radiative transitions in oxygen and, as such, arguably provide one of the final chapters in describing a system that has challenged the scientific community for years.
引用
收藏
页码:8285 / 8296
页数:12
相关论文
共 58 条
[1]   LIFETIME OF SINGLET OXYGEN IN LIQUID SOLUTION [J].
ADAMS, DR ;
WILKINSON, F .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS II, 1972, 68 (04) :586-+
[2]   Absorption spectrum of singlet oxygen (a1Δg→b1Σg+) in D2O:: Enabling the test of a model for the effect of solvent on oxygen's radiative transitions [J].
Andersen, LK ;
Ogilby, PR .
JOURNAL OF PHYSICAL CHEMISTRY A, 2002, 106 (46) :11064-11069
[3]  
Arnbjerg J, 2007, J PHYS CHEM A, V111, P5756, DOI 10.1021/jp0711971
[4]   Two-photon photosensitized production of singlet oxygen: Optical and optoacoustic characterization of absolute two-photon absorption cross sections for standard sensitizers in different solvents [J].
Arnbjerg, Jacob ;
Johnsen, Mette ;
Frederiksen, Peter K. ;
Braslavsky, Silvia E. ;
Ogilby, Peter R. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2006, 110 (23) :7375-7385
[5]   THE SOLUBILITY OF OXYGEN AND OZONE IN LIQUIDS [J].
BATTINO, R ;
RETTICH, TR ;
TOMINAGA, T .
JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1983, 12 (02) :163-178
[6]   EFFECT OF THE PEPTIDE-BOND ON THE SINGLET-MOLECULAR-OXYGEN-MEDIATED SENSITIZED PHOTOOXIDATION OF TYROSINE AND TRYPTOPHAN DIPEPTIDES - A KINETIC-STUDY [J].
BERTOLOTTI, SG ;
GARCIA, NA ;
ARGUELLO, GA .
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY B-BIOLOGY, 1991, 10 (1-2) :57-70
[7]   Solvent-dependent singlet oxygen lifetimes: temperature effects implicate tunneling and charge-transfer interactions [J].
Bregnhoj, Mikkel ;
Westberg, Michael ;
Jensen, Frank ;
Ogilby, Peter R. .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2016, 18 (33) :22946-22961
[8]   Effect of Solvent on the O2(a1Δg) →O2(b1Σg+) Absorption Coefficient [J].
Bregnhoj, Mikkel ;
Ogilby, Peter R. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2015, 119 (35) :9236-9243
[9]   Direct 765 nm Optical Excitation of Molecular Oxygen in Solution and in Single Mammalian Cells [J].
Bregnhoj, Mikkel ;
Blazquez-Castro, Alfonso ;
Westberg, Michael ;
Breitenbach, Thomas ;
Ogilby, Peter R. .
JOURNAL OF PHYSICAL CHEMISTRY B, 2015, 119 (17) :5422-5429
[10]   Direct spectroscopic evidence of photosensitized O-2 765 nm ((1)Sigma(+)(g)->(3)Sigma(-)(g)) and O-2 dimol 634 and 703 nm (((1)Delta(g))(2)->((3)Sigma(-)(g))(2)) vibronic emission in solution [J].
Chou, PT ;
Wei, GT ;
Lin, CH ;
Wei, CY ;
Chang, CH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (12) :3031-3032