Comparison of time-dependent density-functional theory and coupled cluster theory for the calculation of the optical rotations of chiral molecules

The Journal of Physical Chemistry. a
T Daniel Crawford, P J Stephens

Abstract

A comparison of the abilities of time-dependent density-functional theory (TDDFT) and coupled cluster (CC) theory to reproduce experimental sodium D-line specific rotations for 13 conformationally rigid organic molecules is reported. The test set includes alkanes, alkenes, and ketones with known absolute configurations. TDDFT calculations make use of gauge-including atomic orbitals and give origin-independent specific rotations. CC rotations are computed using both the origin-independent dipole-velocity and origin-dependent dipole-length representations. The mean absolute deviations of calculated and experimental rotations are of comparable magnitudes for all three methods. The origin-independent DFT and CC methods give the same sign of [alpha]D for every molecule except norbornanone. For every large-rotation ketone and alkene for which DFT and CC yield the incorrect sign as compared to liquid-phase experimental data, the corresponding optical rotatory dispersion (ORD) curve is bisignate, suggesting that the two models cannot reliably reproduce the relative excitation energies and antagonistic rotational strengths of multiple competing electronic states that contribute to the total long-wavelength rotation. Several potential so...Continue Reading

References

Jul 29, 2003·Chirality·Prasad L PolavarapuFeng Wang
Aug 12, 2004·The Journal of Chemical Physics·Mary C TamT Daniel Crawford
Feb 3, 2005·Journal of the American Chemical Society·T Daniel CrawfordHenrik Koch
Dec 22, 2005·The Journal of Physical Chemistry. a·Shaun M WilsonPatrick H Vaccaro
Feb 10, 2006·The Journal of Physical Chemistry. a·Mary C Tam, T Daniel Crawford
Jun 16, 2006·The Journal of Physical Chemistry. a·Timothy D KowalczykT Daniel Crawford
Oct 31, 2006·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Parag MukhopadhyayDavid N Beratan
Mar 31, 2007·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Prasad L Polavarapu
Apr 11, 2007·Journal of Computational Chemistry·T Daniel CrawfordWesley D Allen
Jul 25, 2007·Angewandte Chemie·Parag MukhopadhyayDavid N Beratan
Nov 8, 2007·The Journal of Physical Chemistry. a·T Daniel CrawfordMicah L Abrams

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Citations

Jan 13, 2012·Chemical Reviews·Trygve HelgakerKenneth Ruud
Jan 29, 2009·The Journal of Chemical Physics·Thomas Bondo PedersenKenneth Ruud
Oct 2, 2012·The Journal of Chemical Physics·Enrico Benassi, Stefano Corni
Nov 7, 2012·The Journal of Chemical Physics·Jefferson E Bates, Filipp Furche
Mar 27, 2012·The Journal of Chemical Physics·Jason LambertT Daniel Crawford
Dec 18, 2015·Journal of Chemical Theory and Computation·Shokouh HaghdaniHenrik Koch
Dec 23, 2015·Journal of the American Chemical Society·Veronica L MurphyBart Kahr
Dec 3, 2015·Journal of Chemical Theory and Computation·Harley R McAlexander, T Daniel Crawford
Dec 17, 2009·Chirality·Ruthanne Hassey-ParadiseMichael D Barnes
Nov 18, 2015·Journal of Chemical Theory and Computation·T Daniel CrawfordLucas Visscher
Jul 15, 2015·The Journal of Physical Chemistry. a·Marco Caricato
Mar 24, 2015·Journal of the American Chemical Society·Veronica L Murphy, Bart Kahr
Jun 15, 2016·Journal of Chemical Theory and Computation·Benjamin FiedlerJoachim Friedrich
Oct 13, 2012·The Journal of Physical Chemistry. a·R Vijay, Prasad L Polavarapu
Dec 5, 2013·The Journal of Physical Chemistry. a·R Vijay, Prasad L Polavarapu
Mar 28, 2013·The Journal of Physical Chemistry. B·Anna PikulskaMagdalena Pecul
Aug 11, 2011·The Journal of Physical Chemistry. a·Monika SrebroJochen Autschbach
Jul 28, 2011·The Journal of Physical Chemistry. a·Taylor J Mach, T Daniel Crawford
Jul 29, 2011·Journal of the American Chemical Society·Veronica L Murphy, Bart Kahr
Jun 15, 2012·The Journal of Physical Chemistry. a·Yoshito NakaiYoshihisa Inoue
Sep 16, 2011·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·T Daniel Crawford, Kenneth Ruud
May 29, 2009·Physical Chemistry Chemical Physics : PCCP·Daniele VarsanoAngel Rubio
Sep 25, 2009·Journal of Computational Chemistry·Angelika BaranowskaAndrzej J Sadlej
Jan 1, 2014·Angewandte Chemie·Priyanka LahiriT Daniel Crawford
Jun 6, 2013·Journal of Computational Chemistry·Angelika Baranowska-Łączkowska, Krzysztof Z Łączkowski
May 18, 2020·The Journal of Chemical Physics·Daniel G A SmithC David Sherrill
May 1, 2012·Physical Chemistry Chemical Physics : PCCP·Harley R McAlexanderT Daniel Crawford
May 4, 2017·Annual Review of Physical Chemistry·Monika Srebro-Hooper, Jochen Autschbach
Sep 29, 2011·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Jochen Autschbach
Oct 24, 2020·The Journal of Chemical Physics·Marco Caricato
Feb 3, 2021·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Ramiro S Galeano CarranoStephan P A Sauer
Sep 13, 2008·The Journal of Physical Chemistry. a·Volkan EdizDavid Yaron

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