Spectroscopic signatures from first principles calculations [Elektronische Ressource] : from surface adsorbates to liquids and polymers / vorgelegt von Tatiana Murakhtina

1.61.2Spectroscopic Signatures from First PrinciplesCalculations: from surface adsorbates to liquids andpolymersDissertationzur Erlangung des Grades”Doktor der Naturwissenschaften”dem Fachbereich Physikder Johannes Gutenberg-Universit¨at Mainzvorgelegt vonTatiana Murakhtinageboren in Udarnik, RussiaMainz 200712Contents1 Introduction 32 Density functional theory (DFT) 112.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112.2 Born-Oppenheimer approximation . . . . . . . . . . . . . . . . . . 122.3 Hohenberg-Kohn and Kohn-Sham formalism . . . . . . . . . . . . 152.4 Exchange-correlation functionals . . . . . . . . . . . . . . . . . . . 202.5 Pseudopotential approximation . . . . . . . . . . . . . . . . . . . 222.6 Plane wave representation . . . . . . . . . . . . . . . . . . . . . . 242.7 Car-Parrinello molecular dynamics (CPMD) . . . . . . . . . . . . 272.8 Treating metals: DFT with fractional occupation numbers . . . . 293 Spectroscopic properties from density functional theory 333.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333.2 IR frequencies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343.2.1 Normal modes . . . . . . . . . . . . . . . . . . . . . . . . . 343.2.2 Change in molecular dipole moment . . . . . . . . . . . . . 363.2.3 Dynamical matrix . . . . . . . . . . . . . . . . . . . . . . . 373.3 NMR chemical shifts . . . . . . . . . . . . . . . . . . . . . . . . . 403.