New basis sets for the evaluation of interaction‐induced electric properties in hydrogen‐bonded complexes

Baranowska-Łączkowska, Angelika; Fernández, Berta; Zaleśny, Robert

doi:10.1002/jcc.23124

Cited by 13 publications

(11 citation statements)

References 55 publications

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“…VP-EDS calculations were carried out using a modified version of the GAMESS (US) program. 85,86 Baranowska et al performed the assessment of basis sets on the electronic excess properties [26][27][28]40,43,44 and suggested that the use of basis sets specifically tailored for such type of calculations (for the analysis of schemes for eliminating the basis set superposition error in calculations of the properties in question we refer to Refs 30,87,88). However, as demonstrated recently by some of the present authors, property-oriented basis sets are not always the best choice to predict the nuclear relaxation (hyper)polarizabilities.…”

Section: Software and Computational Detailsmentioning

confidence: 99%

Partitioning of interaction-induced nonlinear optical properties of molecular complexes. I. Hydrogen-bonded systems

Zaleśny

Medveď

Góra

et al. 2018

Phys. Chem. Chem. Phys.

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Understanding the effects of different fundamental intermolecular interactions on nonlinear optical properties is crucial for proposing efficient strategies to obtain new materials with tailored properties. In this study, we computed the electronic and vibrational (hyper)polarizabilities of ten hydrogen-bonded molecular complexes employing the MP2, CCSD and CCSD(T) methods combined with the aug-cc-pVTZ basis set. The vibrational contributions to hyperpolarizabilities included nuclear-relaxation anharmonic corrections. The effect of intermolecular interactions was analyzed in terms of excess properties, which are defined as the difference between a property of the complex and the net properties of the noninteracting subsystems. Considering systems covering a wide range of hydrogen bond strengths, the electronic and vibrational excess (hyper)polarizabilities were decomposed into different interaction energy contributions (electrostatic, exchange, induction and dispersion). This systematic study, the very first of this kind, revealed that the physical origins of the electronic and vibrational excess properties are completely different. In the case of vibrational contributions, the decomposition pattern is very similar for the polarizability and first and second hyperpolarizabilities. The exchange contributions to excess vibrational properties are the largest and they have an opposite sign to the electrostatic, induction and dispersion terms. On the other hand, no general patterns can be established for the electronic excess properties.

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Section: Software and Computational Detailsmentioning

confidence: 99%

Partitioning of interaction-induced nonlinear optical properties of molecular complexes. I. Hydrogen-bonded systems

Zaleśny

Medveď

Góra

et al. 2018

Phys. Chem. Chem. Phys.

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“…In the case of resonant NLO properties of molecules, like two-photon absorption, the treatment of vibrational contributions using DFT may lead to catastrophic predictions of vibrationally resolved spectra. , Let us recall that the nonresonant vibrational contributions to hyperpolarizability were in many cases found to be of the same magnitude or even larger than their electronic counterparts. − As a natural step toward more complex systems, the electronic NLO properties of various types of weakly bound systems including hydrogen-bonded and van der Waals complexes were intensively studied by high-level post-Hartree–Fock ab initio as well as DFT methods. ,,− It was found that the properties of hydrogen bonded systems can be satisfactorily described by LC-DFAs and also by some global hybrids (e.g., M06-2X) . In the case of van der Waals systems, these methods also performed well provided that the geometries used in the property calculations were optimized taking into account the dispersion interaction. , The good performance of LC-DFAs could be traced back not only to an improved description of the NLO properties of the individual subsystems but also to a better description of the interaction-induced ( excess ) component of NLO properties involving the effects of intermolecular interactions in the complex …”

Section: Introductionmentioning

confidence: 99%

Can Density Functional Theory Be Trusted for High-Order Electric Properties? The Case of Hydrogen-Bonded Complexes

Zaleśny

Medveď

Sitkiewicz

et al. 2019

J. Chem. Theory Comput.

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This work reports on an extensive assessment of the performance of a wide palette of density functional approximations in predicting the (high-order) electric properties of hydrogen-bonded complexes. To this end, we compute the electronic and vibrational contributions to the electric polarizability and the first and second hyperpolarizabilities, using the CCSD(T)/aug-cc-pVTZ level of theory as reference. For all the studied properties, the average absolute errors below 20% can only be obtained using the CAM-B3LYP functional, while LC-BLYP and MN15 are shown to be only slightly less accurate (average absolute errors not exceeding 30%). Among Minnesota density functionals, i.e., M06, M06-2X, and MN15, we only recommend the latter one, which quite accurately predicts the electronic and vibrational (hyper)polarizabilities. We also analyze the optimal tuning of the range-separation parameter μ for the LC-BLYP functional, finding that this approach does not bring any systematic improvement in the predictions of electronic and vibrational (hyper)polarizabilities and the accuracy of computed properties is largely system-dependent. Finally, we report huge errors in predicting the vibrational second hyperpolarizability by ωB97X, M06, and M06-2X functionals. Based on the explicit evaluation of anharmonic terms contributing to the second hyperpolarizability, this failure is traced down to a poor determination of third-and fourth-order energy derivatives with respect to normal modes. These results reveal serious flaws of some density functional approximations and suggest caution in selecting the appropriate functional to calculate not only electronic and vibrational (hyper)polarizabilities but also other molecular properties that contain vibrational anharmonic contributions.

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“…Despite the small size, already the LPol‐ds basis set—the smallest among the LPol‐n sets—gives electric property results very close to those yielded by traditional basis sets of larger size, thus enabling accurate calculations for systems larger than previously. Excellent performance of the LPol‐n sets is reported for linear and nonlinear electric properties of isolated systems, as well as interaction‐induced electric properties in hydrogen‐bonded systems and van der Waals complexes …”

Section: Introductionmentioning

confidence: 99%

The ORP basis set designed for optical rotation calculations

Baranowska-Łączkowska¹,

Łączkowski

2013

J. Comput. Chem.

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Details of generation of the optical rotation prediction (ORP) basis set developed for accurate optical rotation (OR) calculations are presented. Specific rotation calculations carried out at the density functional theory (DFT) level for model chiral methane molecule, fluorooxirane, methyloxirane, and dimethylmethylenecyclopropane reveal that the ORP set outperforms larger basis sets, among them the aug-cc-pVTZ basis set of Dunning (J. Chem. Phys. 1989, 90, 1007) and the aug-pc-2 basis set of Jensen (J. Chem. Phys. 2002, 117, 9234; J. Chem. Theory Comput. 2008, 4, 719). It is shown to be an attractive choice also in the case of larger systems, namely norbornanone, β-pinene, trans-pinane, and nopinone. The ORP basis set is further used in OR calculations for 24 other systems, and the results are compared to the aug-cc-pVDZ values. Whenever large discrepancies of results are observed, the ORP values are in an excellent agreement with the aug-cc-pVTZ results. The ORP basis set enables accurate specific rotation calculations at a reduced cost and thus can be recommended for routine DFT OR calculations, also for large and conformationally flexible molecules.

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New basis sets for the evaluation of interaction‐induced electric properties in hydrogen‐bonded complexes

Cited by 13 publications

References 55 publications

Partitioning of interaction-induced nonlinear optical properties of molecular complexes. I. Hydrogen-bonded systems

Partitioning of interaction-induced nonlinear optical properties of molecular complexes. I. Hydrogen-bonded systems

Can Density Functional Theory Be Trusted for High-Order Electric Properties? The Case of Hydrogen-Bonded Complexes

The ORP basis set designed for optical rotation calculations

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