eprintid: 25375
rev_number: 19
userid: 1419
dir: disk0/00/02/53/75
datestamp: 2015-07-22 14:51:40
lastmod: 2019-02-02 15:56:55
status_changed: 2015-07-22 14:51:40
type: article
metadata_visibility: show
item_issues_count: 0
eprint_status: archive
creators_name: Kondru, RK
creators_name: Wipf, P
creators_name: Beratan, DN
creators_email: 
creators_email: pwipf@pitt.edu
creators_email: 
creators_id: 
creators_id: PWIPF
creators_id: 
title: Structural and Conformational Dependence of Optical Rotation Angles
ispublished: pub
divisions: sch_as_chemistry
full_text_status: public
abstract: The ability to compute and to interpret optical rotation angles of chiral molecules is of great value in assigning relative and absolute stereochemistry. The molar rotations for an indoline and an azetidine, as well as for menthol and menthone, were calculated using ab inito methods and compared to the experimental values. In one case the calculated rotation angle allowed the assignment of the absolute configuration of a heterocycle of unknown stereochemistry. The critical importance of Boltzmann averaging of conformers for reliable prediction of the optical rotation angle was established. Comparisons between static-field and time-dependent methods were made pointing to the limits and validity of the methods as electronic resonance is approached. A protocol analogous to population analysis was used to analyze atomic contributions to the rotation angle in specific conformers. The combination of atomic contribution maps and conformational analysis may provide an indirect tool to assist in three-dimensional structure determination.
date: 1999-08-19
date_type: published
publication: Journal of Physical Chemistry A
volume: 103
number: 33
pagerange: 6603 - 6611
refereed: TRUE
issn: 1089-5639
id_number: 10.1021/jp990697e
citation:   Kondru, RK and Wipf, P and Beratan, DN  (1999) Structural and Conformational Dependence of Optical Rotation Angles.  Journal of Physical Chemistry A, 103 (33).  6603 - 6611.  ISSN 1089-5639     
document_url: http://d-scholarship-dev.library.pitt.edu/25375/1/licence.txt