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Quadratic Response Properties from TDDFT: Trials and Tribulations

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [2];  [3]
  1. Univ. of California, Irvine, CA (United States); University of California, Irvine
  2. Univ. of California, Irvine, CA (United States); Harvard Univ., Cambridge, MA (United States)
  3. Univ. of California, Irvine, CA (United States)
+ Show Author Affiliations
Here, we report on the efficient TURBOMOLE implementation of quadratic response properties within the time-dependent density functional theory (TDDFT) context that includes the static and dynamic dipole hyperpolarizability, ground-to-excited-state two-photon absorption amplitudes (through a single residue) and state-to-state one-photon absorption amplitudes (through a double residue). Our implementation makes full use of arbitrary (including non-Abelian) point-group symmetry as well as permutational symmetry and enables the calculation of nonlinear properties with hybrid density functionals for molecules with hundreds of atoms and thousands of basis functions at a cost that is a fixed multiple of the cost of the corresponding linear properties. Using the PBE0 hybrid density functional, we show that excited-state absorption spectra computed within the pseudowavefunction approach contain the qualitative features of transient absorption spectra tracking excimer formation in perylene diimide dimers, two-photon absorption cross sections for a series of highly twisted fused porphyrin chains are semiquantitatively reproduced, and the computed dynamic hyperpolarizability of several calix[4]arene stereoisomers yield simulated hyper-Raleigh scattering signals consistent with experiment. In addition, we show that the incorrect pole structure of adiabatic TDDFT properties can cause incorrect excited-state absorption spectra and overly resonant hyperpolarizabilities, and discuss possible remedies.
Research Organization:
Univ. of California, Irvine, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0018352
OSTI ID:
2281918
Alternate ID(s):
OSTI ID: 1539132
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 2 Vol. 14; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
Absorption spectroscopy
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Optical properties
Polarizability