Atomic partition of the optical rotatory power of methylhydroperoxide

8 pages, 8 figures, 3 tables.-- PACS: 33.55.+b; 33.15.Bh; 33.15.Kr; 31.15.xrWe applied a methodology capable of resolving the optical rotatory power into atomic contributions. The individual atomic contributions to the optical rotatory power and molecular chirality of the methylhydroperoxide are obtained via a canonical transformation of the Hamiltonian by which the electric dipolar moment operator is transformed to the acceleration gauge formalism and the magnetic dipolar moment operator to the torque formalism. The gross atomic isotropic contributions have been evaluated for the carbon, the nonequivalent oxygen, and the nonequivalent hydrogen atoms of methylhydroperoxide, employing a very large Gaussian basis set which is close to the Hartree-Fock limit.This work was carried out with financial support from the Ministerio de Ciencia y Tecnología of Spain (Project No. CTQ2006-14487-C02-01/BQU ) and Comunidad Autónoma de Madrid (Project MADRISOLAR, Ref. S-0505/PPQ/ 0225). Thanks are given to the CTI (CSIC) and DCSC for allocation of computer time. M.S. thanks the IQM for the financial support while visiting this institution. Financial support from Universidad de Buenos Aires, CONICET, and from the Danish Research Council (FNU) is gratefully acknowledged.Peer reviewe

Atomic partition of the optical rotatory power of methylhydroperoxide

8 pages, 8 figures, 3 tables.-- PACS: 33.55.+b; 33.15.Bh; 33.15.Kr; 31.15.xrWe applied a methodology capable of resolving the optical rotatory power into atomic contributions. The individual atomic contributions to the optical rotatory power and molecular chirality of the methylhydroperoxide are obtained via a canonical transformation of the Hamiltonian by which the electric dipolar moment operator is transformed to the acceleration gauge formalism and the magnetic dipolar moment operator to the torque formalism. The gross atomic isotropic contributions have been evaluated for the carbon, the nonequivalent oxygen, and the nonequivalent hydrogen atoms of methylhydroperoxide, employing a very large Gaussian basis set which is close to the Hartree-Fock limit.This work was carried out with financial support from the Ministerio de Ciencia y Tecnología of Spain (Project No. CTQ2006-14487-C02-01/BQU ) and Comunidad Autónoma de Madrid (Project MADRISOLAR, Ref. S-0505/PPQ/ 0225). Thanks are given to the CTI (CSIC) and DCSC for allocation of computer time. M.S. thanks the IQM for the financial support while visiting this institution. Financial support from Universidad de Buenos Aires, CONICET, and from the Danish Research Council (FNU) is gratefully acknowledged.Peer reviewe