The Current State of Ab Initio Calculations of Optical Rotation and Electronic Circular Dichroism Spectra

T. Daniel Crawford* and Mary C. Tam
Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061
Micah L. Abrams
Department of Chemistry, University of Central Arkansas, Conway, Arkansas 72035
J. Phys. Chem. A, 2007, 111 (48), pp 12057–12068
DOI: 10.1021/jp075046u
Publication Date (Web): November 7, 2007
Copyright © 2007 American Chemical Society

T. Daniel Crawford is an associate professor of chemistry at Virginia Tech. He received his B.S. in chemistry from Duke University in 1992 and his Ph.D. from the University of Georgia's Center for Computational Quantum Chemistry in 1996 under the direction of Prof. Fritz Schaefer. Prior to joining the faculty at Virginia Tech in 2000, he carried out postdoctoral research at the University of Texas with Prof. John F. Stanton. He holds a joint faculty appointment with Oak Ridge National Laboratory, and his research interests currently focus on the development of high-accuracy quantum chemical models for large, chiral molecules.

Mary C. Tam received her B.S. degree in physics and chemistry from Frostburg State University in 2001 and her Ph.D. in physical chemistry from Virginia Tech in 2006. She joined the faculty at Roanoke College in 2006 as a Visiting Assistant Professor of Chemistry. Her research interests include theoretical calculations of optical rotation and enhancing computational chemistry education at the undergraduate level.  

Micah L. Abrams received his Ph.D. from the Georgia Institute of Technology in 2005 under the direction of C. David Sherrill. After postdoctoral research at Virginia Tech, he accepted a position as an assistant professor at his alma mater, the University of Central Arkansas. His research interests include electronic structure theory, computational molecular spectroscopy, and transition metal catalysis.

Physical Organic Chemistry

Abstract

The current ability of ab initio models to compute chiroptical properties such as optical rotatory dispersion and electronic circular dichroism spectra is reviewed. Comparison between coupled cluster linear response theory and experimental data (both gas and liquid phase) yields encouraging results for small to medium-sized chiral molecules including rigid species such as (S)-2-chloropropionitrile and (P)-[4]triangulane, as well as conformationally flexible molecules such as (R)-epichlorohydrin. More problematic comparisons are offered by (S)-methyloxirane, (S)-methylthiirane, and (1S,4S)-norbornenone, for which the comparison between theory and experiment is much poorer. The impact of basis-set incompleteness, electron correlation, zero-point vibration, and temperature are discussed. In addition, future prospects and obstacles for the development of efficient and reliable quantum chemical models of optical activity are discussed, including the problem of gauge invariance, scaling of the coupled cluster approach with system size, and solvation.

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History

  • Published In Issue December 06, 2007
  • Received June 28, 2007
    Revised August 25, 2007

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