EXPERIMENTAL CIRCULAR-DICHROISM AND VUV SPECTRA OF SUBSTITUTED OXIRANES AND THIIRANES

被引：25

作者：

BREEST, A

OCHMANN, P

PULM, F

GODDERZ, KH

CARNELL, M

HORMES, J

机构：

[1] Physikalisches Institut der Universitat Bonn, Bonn, FR, 53115

[2] Institut fur Physikalische Chemie und Theoretische Chemie der Universitat Bonn, Bonn, FR, 53115

来源：

MOLECULAR PHYSICS | 1994年 / 82卷 / 03期

关键词：

D O I：

10.1080/00268979400100404

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：

Highly resolved circular dichroism spectroscopy of alkyl-substituted oxirane and thiirane chromophores was investigated in the vacuum ultraviolet region up to 9.0 eV (138 nm) using synchrotron radiation. Comparison of the gas phase and liquid phase spectra, along with results from theoretical calculations, could confirm the predicted Rydberg character of some excited states including their fine structures. The n(O) --> R(3d) Rydberg transitions in chiral methyloxirane and the predicted n(S) --> sigma* valence transition of (S, S)-(-)-(2,3)-dimethylthiirane were detected for the first time. It could be shown that the quadrant rule for the first state previously verified for some chiral oxiranes also holds for (R)-(-)-1,2-epoxy-3-methyl-butane and (R)-(-)-1,2-epoxy-4-methyl-pentane and is found to be expandable for thiiranes. The first ns Rydberg transitions of dimethyloxirane could be fitted to a term formula.

引用

页码：539 / 551

页数：13

共 19 条

[11] A CIRCULAR-DICHROISM STUDY OF THE OXIRANE CHROMOPHORE
GEDANKEN, A
SCHURIG, V
[J]. JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (06) : 1324 - 1327
[12] CHIRALITY RULE FOR SUBSTITUTED OXIRANES
GEDANKEN, A
HINTZER, K
SCHURIG, V
[J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1984, (23) : 1615 - 1616
[13] KOPPENHOEFER B, 1982, SYNTHESIS-STUTTGART, P316
[14] MCALDUFF EJ, CAN J CHEM, V55, P318
[15] Moore C. E., 1949, 467 US NBS, V1
[16] POLAVARAPU PL, 1985, J CHEM PHYS, V4, P1705
[17] Robin M. B., 1974, HIGHER EXCITED STATE, V1
[18] CIRCULAR-DICHROISM OF OXIRANES - AN INDEPENDENT SYSTEMS PERTURBATION APPROACH
RODGER, A
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (18) : 5941 - 5945
[19] Velluz L., 1965, OPTICAL CIRCULAR DIC

← 1 2 →