Journal article
Authors list: Baraban, Joshua H.; Changala, P. Bryan; Mellau, Georg Ch.; Stanton, John F.; Merer, Anthony J.; Field, Robert W.
Publication year: 2015
Pages: 1338-1342
Journal: Science
Volume number: 350
Issue number: 6266
ISSN: 0036-8075
eISSN: 1095-9203
Open access status: Green
DOI Link: https://doi.org/10.1126/science.aac9668
Publisher: American Association for the Advancement of Science
Abstract:
Transition state theory is central to our understanding of chemical reaction dynamics. We demonstrate amethod for extracting transition state energies and properties froma characteristic pattern found in frequency-domain spectra of isomerizing systems. This pattern-a dip in the spacings of certain barrier-proximal vibrational levels-can be understood using the concept of effective frequency, omega(eff). The method is applied to the cis-trans conformational change in the S-1 state of C2H2 and the bond-breaking HCN-HNC isomerization. In both cases, the barrier heights derived from spectroscopic data agree extremely well with previous ab initio calculations. We also show that it is possible to distinguish between vibrational modes that are actively involved in the isomerization process and those that are passive bystanders.
Citation Styles
Harvard Citation style: Baraban, J., Changala, P., Mellau, G., Stanton, J., Merer, A. and Field, R. (2015) Spectroscopic characterization of isomerization transition states, Science, 350(6266), pp. 1338-1342. https://doi.org/10.1126/science.aac9668
APA Citation style: Baraban, J., Changala, P., Mellau, G., Stanton, J., Merer, A., & Field, R. (2015). Spectroscopic characterization of isomerization transition states. Science. 350(6266), 1338-1342. https://doi.org/10.1126/science.aac9668
Keywords
(A)OVER-TILDE(1)A(U) STATE; DIATOMIC-MOLECULES; HCN; ROTATION; VIBRATIONAL SPACINGS
