On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide
The chirality of molecules expresses itself, for example, in the fact that a solution of a chiral molecule rotates the plane of linear polarised light. The underlying molecular property is the optical rotatory power (ORP) tensor, which according to time-dependent perturbation theory can be calculate...
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2014
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00268976_v112_n12_p1624_Sanchez http://hdl.handle.net/20.500.12110/paper_00268976_v112_n12_p1624_Sanchez |
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paper:paper_00268976_v112_n12_p1624_Sanchez2023-06-08T14:54:00Z On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide Ferraro, Marta Beatriz atomic contributions chirality density functional theory dimethyl peroxide hydrogen peroxide methyl hydroperoxide optical rotatory power Atoms Chirality Density functional theory Dipole moment Electric properties Functional groups Hydrogen peroxide Molecules Oxidation Peroxides atomic contributions Canonical transformation Exchange-correlation functionals Linear response functions Methyl hydroperoxide Optical rotatory power Time dependent density functional theory Time-dependent perturbation theory Stereochemistry The chirality of molecules expresses itself, for example, in the fact that a solution of a chiral molecule rotates the plane of linear polarised light. The underlying molecular property is the optical rotatory power (ORP) tensor, which according to time-dependent perturbation theory can be calculated as mixed linear response functions of the electric and magnetic dipole moment operators. Applying a canonical transformation of the Hamiltonian, which reformulates the magnetic dipole moment operator in terms of the operator for the torque acting on the electrons, the ORP of a molecule can be partitioned into atomic and group contributions. In the present work, we investigate the transferability of such individual contributions in a series of small, chiral molecules: hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide. The isotropic atomic or group contributions have been evaluated for the hydrogen, oxygen and carbon atoms as well as for the methyl group at the level of time-dependent density functional theory with the B3LYP exchange-correlation functional employing a large Gaussian basis set. We find that the atomic or group contributions are not transferable among these three molecules. © 2014 © 2014 Taylor & Francis. Fil:Ferraro, M.B. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2014 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00268976_v112_n12_p1624_Sanchez http://hdl.handle.net/20.500.12110/paper_00268976_v112_n12_p1624_Sanchez |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
atomic contributions chirality density functional theory dimethyl peroxide hydrogen peroxide methyl hydroperoxide optical rotatory power Atoms Chirality Density functional theory Dipole moment Electric properties Functional groups Hydrogen peroxide Molecules Oxidation Peroxides atomic contributions Canonical transformation Exchange-correlation functionals Linear response functions Methyl hydroperoxide Optical rotatory power Time dependent density functional theory Time-dependent perturbation theory Stereochemistry |
| spellingShingle |
atomic contributions chirality density functional theory dimethyl peroxide hydrogen peroxide methyl hydroperoxide optical rotatory power Atoms Chirality Density functional theory Dipole moment Electric properties Functional groups Hydrogen peroxide Molecules Oxidation Peroxides atomic contributions Canonical transformation Exchange-correlation functionals Linear response functions Methyl hydroperoxide Optical rotatory power Time dependent density functional theory Time-dependent perturbation theory Stereochemistry Ferraro, Marta Beatriz On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide |
| topic_facet |
atomic contributions chirality density functional theory dimethyl peroxide hydrogen peroxide methyl hydroperoxide optical rotatory power Atoms Chirality Density functional theory Dipole moment Electric properties Functional groups Hydrogen peroxide Molecules Oxidation Peroxides atomic contributions Canonical transformation Exchange-correlation functionals Linear response functions Methyl hydroperoxide Optical rotatory power Time dependent density functional theory Time-dependent perturbation theory Stereochemistry |
| description |
The chirality of molecules expresses itself, for example, in the fact that a solution of a chiral molecule rotates the plane of linear polarised light. The underlying molecular property is the optical rotatory power (ORP) tensor, which according to time-dependent perturbation theory can be calculated as mixed linear response functions of the electric and magnetic dipole moment operators. Applying a canonical transformation of the Hamiltonian, which reformulates the magnetic dipole moment operator in terms of the operator for the torque acting on the electrons, the ORP of a molecule can be partitioned into atomic and group contributions. In the present work, we investigate the transferability of such individual contributions in a series of small, chiral molecules: hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide. The isotropic atomic or group contributions have been evaluated for the hydrogen, oxygen and carbon atoms as well as for the methyl group at the level of time-dependent density functional theory with the B3LYP exchange-correlation functional employing a large Gaussian basis set. We find that the atomic or group contributions are not transferable among these three molecules. © 2014 © 2014 Taylor & Francis. |
| author |
Ferraro, Marta Beatriz |
| author_facet |
Ferraro, Marta Beatriz |
| author_sort |
Ferraro, Marta Beatriz |
| title |
On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide |
| title_short |
On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide |
| title_full |
On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide |
| title_fullStr |
On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide |
| title_full_unstemmed |
On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide |
| title_sort |
on the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide |
| publishDate |
2014 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00268976_v112_n12_p1624_Sanchez http://hdl.handle.net/20.500.12110/paper_00268976_v112_n12_p1624_Sanchez |
| work_keys_str_mv |
AT ferraromartabeatriz onthetransferabilityofatomiccontributionstotheopticalrotatorypowerofhydrogenperoxidemethylhydroperoxideanddimethylperoxide |
| _version_ |
1768541553269145600 |