Coupled cluster evaluation of the second and third harmonic scattering responses of small molecules

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The static and dynamic second harmonic (βSHS) and third harmonic (γTHS) scattering hyperpolarizabilities and depolarization ratios of water, carbon tetrachloride, chloroform, dichloromethane, chloromethane, and acetonitrile have been evaluated at the coupled cluster response theory level of approximation. Following two recent publications on their measurements, this is the first quantum chemical investigation on γTHSand on its decomposition into its spherical tensor components. Substantial electron correlation and basis set effects are evidenced for βSHSand γTHSand for their depolarization ratios, and they depend on the nature of the molecule. Then, using the selected CCSD/d-aug-cc-pVDZ level, the chlorinated methane derivatives have been studied, showing that (i) the γTHSresponse is dominated by its isotropic contribution, whereas (ii) for βSHSthe dipolar contribution increases from carbon tetrachloride to dichloromethane, chloroform, chloromethane, and acetonitrile. Comparisons with the experimental data obtained from measurements in liquid phase (i) show that the increase of γTHSwith the number for chlorine atoms is well reproduced by the calculations and (ii) suggest that the solvation effects are smaller for γTHSthan for βSHS.
Original languageEnglish
Article number50
Number of pages11
JournalTheor. Chem. Acc.
Issue number4
Publication statusPublished - 1 Apr 2018


  • first and second hyperpolarizabilities
  • coupled cluster response functions
  • second and third harmonic scattering
  • Second and third harmonic scattering
  • Coupled cluster response functions
  • First and second hyperpolarizabilities


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