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Origin invariant calculation of optical rotation without recourse to London orbitals

Pedersen, Thomas LU ; Koch, H; Boman, L and Sánchez de Meras, A M J (2004) In Chemical Physics Letters 393(4-6). p.319-326
Abstract
We propose an inherently origin invariant formulation of specific optical rotation obtained from the conventional velocity gauge expression by subtracting the static limit from the electric dipole-magnetic dipole polarizability: <<(p) over right arrow, (L) over right arrow >>(omega) --> <<(p) over right arrow, (L) over right arrow >>(omega) - <<(p) over right arrow, (L) over right arrow >>(0). London (gauge including) atomic orbitals are therefore not needed to ensure origin invariance and, consequently, this modified velocity gauge formulation may be employed in conjunction with variational and non-variational quantum chemical methods alike. Sample calculations on S-propylene oxide and... (More)
We propose an inherently origin invariant formulation of specific optical rotation obtained from the conventional velocity gauge expression by subtracting the static limit from the electric dipole-magnetic dipole polarizability: <<(p) over right arrow, (L) over right arrow >>(omega) --> <<(p) over right arrow, (L) over right arrow >>(omega) - <<(p) over right arrow, (L) over right arrow >>(0). London (gauge including) atomic orbitals are therefore not needed to ensure origin invariance and, consequently, this modified velocity gauge formulation may be employed in conjunction with variational and non-variational quantum chemical methods alike. Sample calculations on S-propylene oxide and 3,4-methylenedioxymethamphetamine using self-consistent field and coupled cluster wave functions underline this point and show that the basis set convergence of the modified velocity gauge formulation is similar to the conventional length gauge and London expressions. (C) 2004 Elsevier B.V. All rights reserved. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Chemical Physics Letters
volume
393
issue
4-6
pages
319 - 326
publisher
Elsevier
external identifiers
  • wos:000223043100008
  • scopus:3242889162
ISSN
0009-2614
DOI
10.1016/j.cplett.2004.06.065
language
English
LU publication?
yes
id
f0ccbd8c-a6b7-4a5f-aa2b-8aa2bb84e57b (old id 139623)
date added to LUP
2007-07-17 13:17:02
date last changed
2017-11-19 04:10:15
@article{f0ccbd8c-a6b7-4a5f-aa2b-8aa2bb84e57b,
  abstract     = {We propose an inherently origin invariant formulation of specific optical rotation obtained from the conventional velocity gauge expression by subtracting the static limit from the electric dipole-magnetic dipole polarizability: &lt;&lt;(p) over right arrow, (L) over right arrow &gt;&gt;(omega) --&gt; &lt;&lt;(p) over right arrow, (L) over right arrow &gt;&gt;(omega) - &lt;&lt;(p) over right arrow, (L) over right arrow &gt;&gt;(0). London (gauge including) atomic orbitals are therefore not needed to ensure origin invariance and, consequently, this modified velocity gauge formulation may be employed in conjunction with variational and non-variational quantum chemical methods alike. Sample calculations on S-propylene oxide and 3,4-methylenedioxymethamphetamine using self-consistent field and coupled cluster wave functions underline this point and show that the basis set convergence of the modified velocity gauge formulation is similar to the conventional length gauge and London expressions. (C) 2004 Elsevier B.V. All rights reserved.},
  author       = {Pedersen, Thomas and Koch, H and Boman, L and Sánchez de Meras, A M J},
  issn         = {0009-2614},
  language     = {eng},
  number       = {4-6},
  pages        = {319--326},
  publisher    = {Elsevier},
  series       = {Chemical Physics Letters},
  title        = {Origin invariant calculation of optical rotation without recourse to London orbitals},
  url          = {http://dx.doi.org/10.1016/j.cplett.2004.06.065},
  volume       = {393},
  year         = {2004},
}