Basis Set Dependence of Optical Rotation Calculations with Different Choices of Gauge

Parsons, Taylor; Balduf, Ty; Cheeseman, James R.; Caricato, Marco

doi:10.1021/acs.jpca.2c00201

“…This indicates that this basis set is close to completeness for this system and the calculations approach gauge invariance. 64 The PBC-MVG value in Table III is in very good agreement with the value reported in Ref. 37: 36.1 deg L dm −1 mol −1 (the small discrepancy is due to the extreme sensitivity of this property to unavoidable differences in numerical thresholds between different implementations).…”

Section: B Comparison With Cluster Modelssupporting

confidence: 86%

“…The error for the OR is larger (about 50% if the latest experimental value of −12.3 ± 1.0 deg/mm is considered), but it is consistent with the error for the isotropic OR of molecules at this level of theory. 59,64 The choice of gauge is less important than that of the level of theory as the MVG and LG(OI) results are very close to each other. This is also confirmed by the polar plots representation of the OR tensors in Figure 4-5.…”

Section: Mvgmentioning

confidence: 82%

Derivation and Implementation of the Optical Rotation Tensor for Chiral Crystals

Balduf

¹

,

Caricato

²

2022

Preprint

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This work reports the derivation and implementation of the electric dipole-magnetic dipole and electric dipole- electric quadrupole polarizability tensors at density functional theory level with periodic boundary conditions (DFT-PBC). These tensors are combined to evaluate the Buckingham/Dunn tensor that describes the optical rotation (OR) in oriented chiral systems. We detail several aspects of the derivation of the equations, and present test calculations that verify the correctness of the tensors formulation and of their implementation. The results show that the full OR tensor is completely origin invariant as for molecules and that PBC calculations match molecular cluster calculations on 1D chains. A preliminary investigation on the choice of density functional, basis set, and gauge indicates a similar dependence as for molecules: the functional is the primary factor that determines the OR magnitude, followed by the basis set and to a much smaller extent the choice of gauge. However, diffuse functions may be problematic for PBC calculations even if they are necessary for the molecular case. A comparison with experimental data of OR for the tartaric acid crystal shows reasonable agreement given the level of theory employed. The development presented in this work offers the opportunity to simulate the OR of chiral crystalline materials with general purpose DFT-PBC methods, which in turn may help to understand the role of intermolecular interactions on this sensitive electronic property.

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“…Grimme et al suggested a simplified TDDFT (sTDDFT), which is so cheap to allow many calculations on several snapshots taken from a preliminary molecular dynamics (MD) 8 calculation, or an automated procedure to treat flexible molecules 9 . From a different perspective, Caricato et al have studied the problem of the gauge choice in optical rotation 10–14 . Mennucci et al worked on excitonic models 15 while Cappelli on the chiroptical properties in aqueous solution 16 .…”

Section: Introductionmentioning

confidence: 99%

A computational approach for modeling electronic circular dichroism of solvated chromophores

Monti

¹

,

Stener

²

,

Aschi

³

2022

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The present study consists in a novel computational protocol to model the UV-circular dichroism spectra of solvated species. It makes use of quantum-chemical calculations on a series of conformations of a flexible chromophore or on a series of chromophore/solvent clusters extracted from molecular dynamic simulations. The protocol is described and applied to the aqueous cationic tripeptide GAG + and to the aqueous neutral decapeptide (GVGVP) 2 . The protocol has proven able to: (i) properly consider the conformational motion of solute in the given environment; (ii) give the actual statistical weight of each conformational state; (iii) provide a reliable quantum mechanical method able to reproduce the spectral features. Temperature effects on conformations and spectral properties are properly taken into account. The role of explicit solvent on the conformational analysis and the spectra calculation is discussed. The comparison of the calculated circular dichroism spectra with experimental ones recorded at different temperatures represents a strict validation test of the method.

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“…LG(OI) Exp. 59,64 The choice of gauge is less important than that of the level of theory as the MVG and LG(OI) results are very close to each other. This is also confirmed by the polar plots representation of the OR tensors in Figure 4-5.…”

Section: Mvgmentioning

confidence: 82%

Derivation and Implementation of the Optical Rotation Tensor for Chiral Crystals

Balduf

¹

,

Caricato

²

2022

Preprint

0

View full text Add to dashboard Cite

This work reports the derivation and implementation of the electric dipole-magnetic dipole and electric dipole- electric quadrupole polarizability tensors at density functional theory level with periodic boundary conditions (DFT-PBC). These tensors are combined to evaluate the Buckingham/Dunn tensor that describes the optical rotation (OR) in oriented chiral systems. We detail several aspects of the derivation of the equations, and present test calculations that verify the correctness of the tensors formulation and of their implementation. The results show that the full OR tensor is completely origin invariant as for molecules and that PBC calculations match molecular cluster calculations on 1D chains. A preliminary investigation on the choice of density functional, basis set, and gauge indicates a similar dependence as for molecules: the functional is the primary factor that determines the OR magnitude, followed by the basis set and to a much smaller extent the choice of gauge. However, diffuse functions may be problematic for PBC calculations even if they are necessary for the molecular case. A comparison with experimental data of OR for the tartaric acid crystal shows reasonable agreement given the level of theory employed. The development presented in this work offers the opportunity to simulate the OR of chiral crystalline materials with general purpose DFT-PBC methods, which in turn may help to understand the role of intermolecular interactions on this sensitive electronic property.

show abstract

Basis Set Dependence of Optical Rotation Calculations with Different Choices of Gauge

Cited by 11 publications

References 74 publications

Derivation and Implementation of the Optical Rotation Tensor for Chiral Crystals

Derivation and Implementation of the Optical Rotation Tensor for Chiral Crystals

A computational approach for modeling electronic circular dichroism of solvated chromophores

Derivation and Implementation of the Optical Rotation Tensor for Chiral Crystals

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