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Time‐Dependent Density Functional Theory for Calculating Origin‐Independent Optical Rotation and Rotatory Strength Tensors
Author(s) -
Autschbach Jochen
Publication year - 2011
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201100225
Subject(s) - time dependent density functional theory , density functional theory , tensor (intrinsic definition) , raman optical activity , optical rotation , excitation , chemistry , computational chemistry , computation , molecular physics , physics , spectral line , quantum mechanics , mathematics , geometry , organic chemistry , algorithm
An approach to calculate origin‐independent electronic chiroptical property tensors using time‐dependent density functional theory (TDDFT) and gauge‐including atomic orbital (GIAO) basis sets is evaluated. Computations of origin‐dependent optical rotation tensors and of rotatory strengths needed to simulate circular dichroism spectra are presented. The optical rotation tensor computations employ solutions of coupled perturbed Kohn–Sham equations for a dynamic electric field and a static magnetic field. Because the magnetic field is time independent, the GIAO treatment is somewhat simplified compared to a previously reported method, at some added computational cost if hybrid functionals are employed. GIAO rotatory strengths are also calculated, using transition density matrices from a standard TDDFT excitation energy module. A new implementation in the NWChem quantum chemistry package is employed for representative computations of origin‐invariant chiroptical response tensors for methyloxirane, norbornenone, and the ketosteroid androstadienone. For the steroid molecule the vibrational structure of the CD spectrum is modeled explicitly by using calculated Franck–Condon factors. The agreement with experiment is favorable.