The ORP basis set designed for optical rotation calculations

Baranowska-Łączkowska, Angelika; Łączkowski, Krzysztof Z.

doi:10.1002/jcc.23347

Cited by 26 publications

(64 citation statements)

References 66 publications

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“…As mentioned earlier, the LPol‐ n family recommended for electric property evaluation suffers from strong near‐linear dependence, which leads to removal of a substantial number of functions even in the case of relatively small systems. Contrary, our earlier DFT/B3LYP study revealed that the near‐linear dependence for the ORP basis set is similar to that for other medium‐size basis sets, which means that the use of ORP set in the calculations carried out for larger molecular systems is not likely to lead to numerical problems . In the present work the near‐linear dependence of the R‐ORP basis set functions has been investigated.…”

Section: Resultsmentioning

confidence: 67%

“…It stems from the method of generation of the LPol‐ n sets, resulting in polarization functions having the same exponents as those already present in the source basis set . The LPol‐ n sets are known to suffer from the near‐linear dependence even in the case of relatively small molecules, and the number of functions removed from the total set soon becomes substantial . The removal of the basis functions decreases the size of the basis set in a not fully controlled manner, which in turn may affect the accuracy of investigated system description.…”

Section: Introductionmentioning

confidence: 99%

“…The new basis set contains the same number of functions as the aVDZ set, and thus allows some reduction of the computing cost with respect to the LPol‐ds, TZVPD, and apc2 basis sets recommended in the earlier study for molecular polarizability calculations . It is developed from the VTZ basis set of Ahlrichs and coworkers through addition of the first‐order polarization functions, in a close resemblance to the recently developed ORP set, intended for optical rotation calculations . The ORP basis set has been reported for hydrogen, carbon, nitrogen, oxygen, and fluorine—elements present in a large percentage of molecules investigated using contemporary quantum mechanical methods, and particularly in organic systems.…”

Section: Introductionmentioning

confidence: 99%

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Efficient polarized basis sets for evaluation of static and dynamic molecular electric properties

Baranowska-Łączkowska

2016

Int. J. Quantum Chem.

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New medium size Gaussian-type basis set R-ORP for evaluation of static and dynamic electric properties in molecular systems is presented. It is obtained in a close resemblance to the original ORP basis set, from the source basis set through addition of two first-order polarization functions whose exponent values are optimized with respect to the finite field restricted open-shell Hartree-Fock (ROHF) atomic polarizabilities. As the source set the VTZ basis set of Ahlrichs and coworkers, augmented with additional diffuse functions and contracted to the form [6s/3s] for hydrogen and [11s7p/4s3p] for carbon through fluorine, is chosen. The resulting basis set is of the form [6s2p/3s2p] for hydrogen and [11s7p2d/4s3p2d] for other atoms. Presented basis set is next tested in the CCSD static and dynamic molecular polarizability and hyperpolarizability calculations for a set of ten and four test molecules, respectively, for which very accurate reference data exist. Additionally, the recently developed ORP basis set is employed in the calculations to examine the limits of its applicability. Results are compared to the literature data obtained in both, large and diffuse, as well as reduced-size basis sets. In the case of polarizability calculations, the aug-pc-1 and R-ORP are the optimal choices among the investigated smaller basis sets, with the overall performance of the aug-pc-1 set being better. Among the larger sets, the ORP performs better in the case of average polarizability, while the RMSE values for polarizability anisotropy are practically identical for d-aug-cc-pVDZ and ORP sets. Finally, the R-ORP and ORP basis sets compete other small bases in the evaluation of the first hyperpolarizability in investigated systems.

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Section: Resultsmentioning

confidence: 67%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Efficient polarized basis sets for evaluation of static and dynamic molecular electric properties

Baranowska-Łączkowska

2016

Int. J. Quantum Chem.

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“…It has been only quite recently that the optical rotation prediction (ORP) basis set has been developed by some of the present authors for investigation of specific rotation of organic molecules. 17 The ORP basis set is derived from the VTZ basis set of Ahlrichs et al 18 augmented with one diffuse s-type and one diffuse p-type functions. The ORP basis set has the size very close to the LPol-ds basis set, however it was found to be more resistant to the occurence of linear dependencies in the molecular basis set.…”

Section: Introductionmentioning

confidence: 99%

“…In an attempt to fill this gap, in the present work we investigate electric properties (electronic and vibrational) using the property-oriented Pol and LPol-ds basis sets of Sadlej and co-workers, 10,38 the def2-SVPD and def2-TZVPD sets of Rappoport and Furche, 15 and the ORP basis set reported recently by Baranowska-Łączkowska and Łączkowski. 17 Additionally, we use the aug-cc-pVXZ and d-aug-cc-pVXZ (X=D,T,Q) basis sets of Dunning and co-workers. [1][2][3] We combine these basis sets with the second-order Møller and Plesset perturbation theory (MP2) approach and CCSD(T) method to evaluate the diagonal components of the static electronic dipole polarizability, first and second hyperpolarizabilities.…”

Section: Introductionmentioning

confidence: 99%

Comparison of Property-Oriented Basis Sets for the Computation of Electronic and Nuclear Relaxation Hyperpolarizabilities

Zaleśny

Baranowska-Łączkowska

Medveď

et al. 2015

J. Chem. Theory Comput.

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In the present work, we perform an assessment of several property-oriented atomic basis sets in computing (hyper)polarizabilities with a focus on the vibrational contributions. Our analysis encompasses the Pol and LPol-ds basis sets of Sadlej and co-workers, the def2-SVPD and def2-TZVPD basis sets of Rappoport and Furche, and the ORP basis set of Baranowska-Łączkowska and Łączkowski. Additionally, we use the d-aug-cc-pVQZ and aug-cc-pVTZ basis sets of Dunning and co-workers to determine the reference estimates of the investigated electric properties for small- and medium-sized molecules, respectively. We combine these basis sets with ab initio post-Hartree-Fock quantum-chemistry approaches (including the coupled cluster method) to calculate electronic and nuclear relaxation (hyper)polarizabilities of carbon dioxide, formaldehyde, cis-diazene, and a medium-sized Schiff base. The primary finding of our study is that, among all studied property-oriented basis sets, only the def2-TZVPD and ORP basis sets yield nuclear relaxation (hyper)polarizabilities of small molecules with average absolute errors less than 5.5%. A similar accuracy for the nuclear relaxation (hyper)polarizabilites of the studied systems can also be reached using the aug-cc-pVDZ basis set (5.3%), although for more accurate calculations of vibrational contributions, i.e., average absolute errors less than 1%, the aug-cc-pVTZ basis set is recommended. It was also demonstrated that anharmonic contributions to first and second hyperpolarizabilities of a medium-sized Schiff base are particularly difficult to accurately predict at the correlated level using property-oriented basis sets. For instance, the value of the nuclear relaxation first hyperpolarizability computed at the MP2/def2-TZVPD level of theory is roughly 3 times larger than that determined using the aug-cc-pVTZ basis set. We link the failure of the def2-TZVPD basis set with the difficulties in predicting the first-order field-induced coordinates. On the other hand, the aug-cc-pVDZ and ORP basis sets overestimate the property in question only by roughly 30%. In this study, we also propose a low-cost composite treatment of anharmonicity that relies on the combination of two basis sets, i.e., a large-sized basis set is employed to determine lowest-order derivatives with respect to the field-induced coordinates, and a medium-sized basis set is used to compute the higher-order derivatives. The results of calculations performed at the MP2 level of theory demonstrate that this approximate scheme is very successful at predicting nuclear relaxation hyperpolarizabilities.

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A molecular orbital selection approach for fast calculations of specific rotation with density functional theory

Aharon

Caricato

2019

Chirality

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In this work, we describe a simple approach to select the most important molecular orbitals (MOs) to compute the optical rotation tensor through linear response (LR) Kohn‐Sham density functional theory (KS‐DFT). Taking advantage of the iterative nature of the algorithms commonly used to solve the LR equations, we select the MOs with contributions to the guess perturbed density that are larger than a certain threshold and solve the LR equations with the selected MOs only. We propose two criteria for the selection, and two definitions of the selection threshold. We then test the approach with two functionals (B3LYP and CAM‐B3LYP) and two basis sets (aug‐cc‐pVDZ and aug‐cc‐pVTZ) on a set of 51 organic molecules with specific rotation spanning five orders of magnitude, 100–104 deg (dm−1 (g/mL)−1). We show that this approach indeed can provide very accurate values of specific rotation with estimated speedup that ranges from 2 to 8× with the most conservative selection criterion, and up to 20 to 30× with the intermediate criterion.

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The ORP basis set designed for optical rotation calculations

Cited by 26 publications

References 66 publications

Efficient polarized basis sets for evaluation of static and dynamic molecular electric properties

Efficient polarized basis sets for evaluation of static and dynamic molecular electric properties

Comparison of Property-Oriented Basis Sets for the Computation of Electronic and Nuclear Relaxation Hyperpolarizabilities

A molecular orbital selection approach for fast calculations of specific rotation with density functional theory

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