An analytical derivative procedure for the calculation of vibrational Raman optical activity spectra.
We present an analytical time-dependent Hartree-Fock algorithm for the calculation of the derivatives of the electric dipole-magnetic dipole polarizability with respect to atomic Cartesian coordinates. Combined with analogous procedures to determine the derivatives of the electric dipole-electric dipole and electric dipole-electric quadrupole polarizabilities, it enables a fully analytical evaluation of the three frequency-dependent vibrational Raman optical activity (VROA) invariants within the harmonic approximation. The procedure employs traditional non-London atomic orbitals, and the gauge-origin dependence of the VROA intensities has, therefore, been assessed for the commonly used aug-cc-pVDZ and rDPS:3-21G basis sets.
Laboratoire de Chimie Theorique Appliquée, Groupe de Chimie Physique, Facultés Universitaires Notre-Dame de la Paix, Rue de Bruxelles 61, Namur, Belgium. vincent.liegeois@fundp.ac.be
Vincent
V
Liégeois
Kenneth
K
Ruud
Benoît
B
Champagne
D000465:Algorithms; D003198:Computer Simulation; D004583:Electrons; D004852:Epoxy Compounds / Q000737:chemistry*; D011789:Quantum Theory; D013059:Spectrum Analysis, Raman / Q000379:methods*; D013997:Time Factors; D014732:Vibration
D004852:Epoxy Compounds; C009068:propylene oxide