We present a fully analytical formulation for calculating Raman intensities of crystalline periodic systems using a local basis set. Numerical differentiation with respect to atomic coordinates and with respect to wavevectors is entirely avoided as is the determination of crystal orbital coefficient derivatives with respect to nuclear displacements. Instead, our method utilizes the orbital energy-weighted density matrix and is based on the self-consistent solution of first- and second-order Coupled Perturbed Hartree-Fock/Kohn-Sham equations for the electronic response to external electric fields at the equilibrium geometry. This method has also been implemented in the CRYSTAL program, which uses a Gaussian type basis set.

Ab initio analytical Raman intensities for periodic systems through a coupled perturbed Hartree-Fock/Kohn-Sham method in an atomic orbital basis. I. Theory

MASCHIO, LORENZO;ORLANDO, Roberto;DOVESI, Roberto
2013

Abstract

We present a fully analytical formulation for calculating Raman intensities of crystalline periodic systems using a local basis set. Numerical differentiation with respect to atomic coordinates and with respect to wavevectors is entirely avoided as is the determination of crystal orbital coefficient derivatives with respect to nuclear displacements. Instead, our method utilizes the orbital energy-weighted density matrix and is based on the self-consistent solution of first- and second-order Coupled Perturbed Hartree-Fock/Kohn-Sham equations for the electronic response to external electric fields at the equilibrium geometry. This method has also been implemented in the CRYSTAL program, which uses a Gaussian type basis set.
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http://scitation.aip.org/content/aip/journal/jcp/139/16/10.1063/1.4824442
ab initio modeling; Raman spectra; coupled perturbed hartree-fock; CRYSTAL
Lorenzo Maschio;Bernard Kirtman;Michel Rérat;Roberto Orlando;Roberto Dovesi
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2318/139236
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