Direct Measurement of Energy Thresholds to Conformational Isomerization in Tryptamine

Science

Volumn 303, Issue 5661, 2004, Pages 1169-1173

  Dian, Brian C ^a,b   Clarkson, Jasper R ^a   Zwier, Timothy S ^a  

^a PURDUE UNIVERSITY   (United States)

^b UNIVERSITY OF VIRGINIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BAND STRUCTURE; CONFORMATIONS; ISOMERIZATION; ISOMERS; SPECTROSCOPIC ANALYSIS;

CONFORMATIONAL MINIMA; ENERGY THRESHOLDS;

AMINES;

TRYPTAMINE; TRYPTAMINE DERIVATIVE;

ENERGY; SPECTROSCOPY;

ARTICLE; CHEMISTRY; CONFORMATION; ENERGY; INFRARED RADIATION; ISOMERISM; ISOMERIZATION; KINETICS; MEASUREMENT; PHOTON; PHYSICAL CHEMISTRY; PRIORITY JOURNAL; SPECTROSCOPY; STIMULATED EMISSION PUMPING; THERMODYNAMICS;

CHEMISTRY, PHYSICAL; ISOMERISM; KINETICS; MOLECULAR CONFORMATION; SPECTRUM ANALYSIS; THERMODYNAMICS; TRYPTAMINES;

EID: 1242284602     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.1093731     Document Type: Article

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19. -1 upper bound in the C→B spectrum on the basis of the relative energies of other barriers shown.
20. Density functional theory calculations at the Becke3LYP/6-31+G(d) level of theory predict barriers for the A-B and A-F isomerizations that are several hundred wavenumbers higher than experiment. However, the computed barriers for A→C(1), A→D, and A→E are close to those measured. This suggests that the pathway for A-B and A-F isomerizations may proceed by some pathway other than the direct one computed.
21. Supported by the National Science Foundation (CHE-0242818). We thank D. W. Pratt and his group for providing the results of their high-resolution spectra on TRA before publication.