Origin invariant calculation of optical rotation without recourse to London orbitals

Pedersen, Thomas Bondo; Koch, Henrik; Boman, Linus; Merás, Alfredo M. J. Sánchez de

doi:10.1016/j.cplett.2004.06.065

Cited by 172 publications

(244 citation statements)

References 24 publications

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“…Investigations are underway regarding inherently origin invariant calculations of specific rotations without resorting to London orbitals for variational as well as nonvariational models. 46 TABLE VIII. Frozen core CC2 specific rotation (͓␣͔ D , in deg ͓dm g/cm 3 ͔ Ϫ1 ) at the sodium D line in length gauge ͑origin at the center of charge͒ for TCO using Cholesky algorithm.…”

Section: Summary and Concluding Remarksmentioning

confidence: 99%

Polarizability and optical rotation calculated from the approximate coupled cluster singles and doubles CC2 linear response theory using Cholesky decompositions

Pedersen

Merás

Koch

2004

The Journal of Chemical Physics

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117

100

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A new implementation of the approximate coupled cluster singles and doubles CC2 linear response model using Cholesky decomposition of the two-electron integrals is presented. Significantly reducing storage demands and computational effort without sacrificing accuracy compared to the conventional model, the algorithm is well suited for large-scale applications. Extensive basis set convergence studies are presented for the static and frequency-dependent electric dipole polarizability of benzene and C 60 , and for the optical rotation of CNOFH 2 and (Ϫ)-trans-cyclooctene ͑TCO͒. The origin-dependence of the optical rotation is calculated and shown to persist for CC2 even at basis set convergence.

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Section: Summary and Concluding Remarksmentioning

confidence: 99%

Polarizability and optical rotation calculated from the approximate coupled cluster singles and doubles CC2 linear response theory using Cholesky decompositions

Pedersen

Merás

Koch

2004

The Journal of Chemical Physics

Self Cite

117

100

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“…The decomposition was shown to give large savings for large basis sets with a variety of theoretical methods: Hartree-Fock (HF), density functional theory (DFT), second order Møller-Plesset perturbation theory (MP2), and the second-order approximate coupled cluster model (CC2) [34]. These implementations in the DALTON program has formed the basis for many computational developments and applications [35][36][37][38][39][40][41][42][43]. The CD strategy has subsequently been implemented in the MOLCAS program [44] for multiconfigurational methods (multiconfigurational self-consistent field (MCSCF) [45] and multiconfigurational second-order perturbation theory (CASPT2) [46]) as well as scaled opposite spin MP2 [47] and coupled cluster (CC) methods [44].…”

Section: Introductionmentioning

confidence: 99%

Cholesky Decomposition Techniques in Electronic Structure Theory

Aquilante

Boman

Boström

et al. 2011

Challenges and Advances in Computational Chemistry and Physics

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We review recently developed methods to efficiently utilize the Cholesky decomposition technique in electronic structure calculations. The review starts with a brief introduction to the basics of the Cholesky decomposition technique. Subsequently, examples of applications of the technique to ab inito procedures are presented. The technique is demonstrated to be a special type of a resolution-of-identity or density-fitting scheme. This is followed by explicit examples of the Cholesky techniques used in orbital localization, computation of the exchange contribution to the Fock matrix, in MP2, gradient calculations, and so-called method specific

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“…The basis set denoted augcc-pVD[T]Z is obtained by using aug-cc-pVDZ on all atoms except those involved in double-or triple-bonds where the aug-cc-pVTZ basis set is used. To ensure origin invariance, gauge including atomic orbitals (GIAOs) 57,58 are used in conjunction with B3LYP, whereas the modified velocity gauge (MVG) formulation 59 is used for the CC2 and CCSD models. In addition, despite its origin-dependence, the length gauge (LG) formulation is used for the CC2 and CCSD calculations; the center of mass is chosen as coordinate origin for these calculations.…”

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confidence: 99%

Gas phase optical rotation calculated from coupled cluster theory with zero‐point vibrational corrections from density functional theory

2009

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Molecular vibrations can have a significant influence on gas phase specific optical rotations. Mainly due to the large number of nuclear degrees of freedom in most chiral molecules, theoretical predictions of vibrational corrections quickly become prohibitively expensive. Here, we investigate an approach in which the purely electronic contribution is calculated at the coupled cluster singles and doubles level, while the zero-point vibrational correction is computed using the less demanding density functional theory (B3LYP functional). By comparing to experimental gas phase results for seven molecules and two wavelengths, we find that the mixed coupled cluster/B3LYP approach performs significantly better than pure B3LYP predictions. In fact, we find that it is more important to use high-level electron correlation for the electronic contribution than to include zero-point vibrational corrections.

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Origin invariant calculation of optical rotation without recourse to London orbitals

Cited by 172 publications

References 24 publications

Polarizability and optical rotation calculated from the approximate coupled cluster singles and doubles CC2 linear response theory using Cholesky decompositions

Polarizability and optical rotation calculated from the approximate coupled cluster singles and doubles CC2 linear response theory using Cholesky decompositions

Cholesky Decomposition Techniques in Electronic Structure Theory

Gas phase optical rotation calculated from coupled cluster theory with zero‐point vibrational corrections from density functional theory

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