Beyond the Rosenfeld Equation: Computation of Vibrational Circular Dichroism Spectra for Anisotropic Solutions

Journal of Chemical Theory and Computation
Dominik SidlerSereina Riniker

Abstract

The difference in absorption of left and right circularly polarized light by chiral molecules can be described by the Rosenfeld equation for isotropic samples. It allows the assignment of the absolute stereochemistry by comparing experimental and computationally derived spectra. Despite the simple form of the Rosenfeld equation, its evaluation in the infrared regime remained challenging, as the contribution from the magnetic dipole operator is zero within the Born-Oppenheimer (BO) approximation. In order to resolve this issue, "beyond BO" theories had to be developed, among which Stephen's magnetic field perturbation (MFP) approach offers a computationally easily accessible form. In this work, optical activity is discussed for cylindrically symmetric solutions, which cannot be described anymore by Rosenfeld's equation due to broken spherical symmetry. Mathematical properties of natural and electric-field induced anisotropies are discussed on the basis of the gauge-independent theoretical framework of Buckingham and Dunn. The issue of achiral noise arising from external field perturbations is considered, and potential remedies are introduced. Natural anisotropic vibrational circular dichroism (VCD) equations are solved numerical...Continue Reading

References

Sep 13, 2001·Journal of the American Chemical Society·K M SpechtD Kahne
Oct 3, 2001·Physical Review Letters·F Rosca-Pruna, M J Vrakking
Jul 23, 2004·The Journal of Chemical Physics·Harald SolheimPer-Olof Astrand
Jul 26, 2006·The Journal of Chemical Physics·Mykhaylo Krykunov, Jochen Autschbach
Oct 10, 2007·Chirality·H D Flack, G Bernardinelli
Jan 18, 2008·Chirality·Stig Allenmark, Jacek Gawronski
Jul 10, 2008·The Journal of Physical Chemistry. a·Valentin Paul NicuEvert Jan Baerends
Jul 17, 2009·Physical Chemistry Chemical Physics : PCCP·Valentin Paul Nicu, Evert Jan Baerends
Sep 28, 2010·Physical Review Letters·Ali AbediE K U Gross
Aug 16, 2011·Physical Chemistry Chemical Physics : PCCP·Valentin Paul Nicu, Evert Jan Baerends
Sep 29, 2011·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Jochen Autschbach
Mar 19, 2013·Physical Review Letters·Dominik PentlehnerHenrik Stapelfeldt
Oct 14, 2014·Wiley Interdisciplinary Reviews. Computational Molecular Science·Kestutis AidasHans Agren
Mar 24, 2015·Journal of the American Chemical Society·Veronica L Murphy, Bart Kahr
Sep 30, 2015·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Carsten Tschierske, Goran Ungar
Dec 10, 2013·Journal of Chemical Theory and Computation·A ScherrerD Sebastiani
Oct 6, 2016·Journal of Chemical Theory and Computation·Tommaso GiovanniniChiara Cappelli
Jul 14, 2018·Angewandte Chemie·Sascha JähnigenDaniel Sebastiani
Jan 13, 2019·Nature Communications·Adam S ChatterleyHenrik Stapelfeldt

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Citations

Jun 3, 2021·Langmuir : the ACS Journal of Surfaces and Colloids·Morgan HesserReinhard Schweitzer-Stenner
Jul 30, 2021·Chemical Communications : Chem Comm·Alexander T MartinBart Kahr

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