TY - JOUR

T1 - On the transferability of atomic contributions to the optical rotatory power of hydrogen peroxide, methyl hydroperoxide and dimethyl peroxide

AU - Sánchez, Marina

AU - Alkorta, Ibon

AU - Elguero, José

AU - Ferraro, Marta B.

AU - Sauer, Stephan P. A.

PY - 2014

Y1 - 2014

N2 - 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.

AB - 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.

KW - atomic contributions

KW - chirality

KW - density functional theory

KW - dimethyl peroxide

KW - hydrogen peroxide

KW - methyl hydroperoxide

KW - optical rotatory power

U2 - 10.1080/00268976.2013.851420

DO - 10.1080/00268976.2013.851420

M3 - Journal article

AN - SCOPUS:84901826822

VL - 112

SP - 1624

EP - 1632

JO - Molecular Physics

JF - Molecular Physics

SN - 0026-8976

IS - 12

ER -