Electronic circular dichroism spectra from the complex polarization propagator

Abstract

The complex linear polarization propagator approach has been applied to the calculation of electronic circular dichroism spectra of 3R-chloro-1-butyne, 3R-methylcyclopentanone, 3S-methylcyclohexanone, 4R-1,1-dimethyl-[3]-(1,2)ferrocenophan-2-on, S-3,3,3',3'-tetramethyl-1,1'-spirobi[3H,2,1]-benzoxaselenole, and the fullerene C84. Using time-dependent Kohn-Sham density functional theory, it is shown that a direct and efficient evaluation of the circular dichroism spectrum can be achieved. The approach allows for the determination of the circular dichroism at an arbitrary wavelength thereby, in a common formulation and implementation, covering the visible, ultraviolet, and x-ray regions of the spectrum. In contrast to traditional methods, the entire manifold of excited states is taken into account in the calculation of the circular dichroism at a given wavelength.

Optically active nanoparticles: Fullerenes, carbon nanotubes, and metal nanoparticles

“…2 show an intensity that is at least 20 times larger than the experimental one [49,58]. These calculated CD spectra are of the same order of magnitude than previous calculations using TDDFT [78,79]. Additionally, they are also of the same order than calculations for other higher fullerenes, such as C 76 and C 78 [60], and the measured CD spectrum for C 76 [50].…”

“…Additionally, they blue shifted by 0.4 eV the calculated excitation energies and used a Gaussian broadening of 0.1 eV in the reported CD spectrum. More recently, Jiemchooroj and Norman [79] also calculated the CD spectrum of this fullerene by employing the complex polarization propagator method, which was implemented in the dalton code, which uses the B3LYP (Becke, threeparameter, Lee-Yang-Parr) hybrid exchange-correlation functional [80,81]. As in our case, both calculations show dissimilarities from the experimental CD curves, including large intensity deviations.…”

“…To understand this chiroptical property of D 2 -C 84 , two previous calculations were performed within TDDFT [78,79]. The first calculated CD spectrum of D 2 -C 84 , by Furche and Ahlrichs [78], was obtained using the BeckePerdew exchange-correlation functional within the turbomole code.…”

Damped response theory description of two-photon absorption

“…The permutation operator was defined in Eq. (18). Considering damped TPA, the nth term will dominate the sum-over-states expressions in Eq.…”

“…Damped linear response properties that have been addressed using damped response theory include one-photon absorption (OPA) spectra and dispersion coefficients, [8][9][10][11][12][13][14][15][16] optical rotation and electronic circular dichroism spectra, [17][18][19][20][21] x-ray absorption and natural circular dichroism spectra, [22][23][24][25][26][27] the dynamic dipole magnetizability, 28 and relativistic linear response functions. 29,30 Damped non-linear molecular properties described by quadratic response theory have been addressed, including Raman scattering, [31][32][33][34][35][36][37][38][39][40][41] the electro-optical Kerr effect and second-harmonic generation, 6 and magnetic circular dichroism.…”