A consistent derivation is given for local field factors to be used for correcting measured or calculated static (hyper)polarizabilities in the condensed phases. We show how local fields should be used in the coupled perturbative Hartree–Fock or finite field methods for calculating these properties, specifically for the direct reaction field (DRF) approach, in which a quantum chemically treated “solute” is embedded in a classical “solvent” mainly containing discrete molecules. The derivation of the local fields is based on a strictly linear response of the classical parts and they are independent of any quantum mechanical method to be used. In applications to two water dimers in two basis sets it is shown that DRF matches fully quantum mechanical results quite well. For acetone in eleven different solvents we find that if the solvent is modeled by only a dielectric continuum (hyper)polarizabilities increase with respect to their vacuum values, while with the discrete model they decrease. We show that the use of the Lorentz field factor for extracting (hyper)polarizabilities from experimental susceptibilities may lead to serious errors.
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8 November 2002
Research Article|
November 08 2002
Polarizabilities in the condensed phase and the local fields problem: A direct reaction field formulation
Piet Th. van Duijnen;
Piet Th. van Duijnen
Theoretical Chemistry, Materials Science Centre, Rijksuniversiteit Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands
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Alex H. de Vries;
Alex H. de Vries
Theoretical Chemistry, Materials Science Centre, Rijksuniversiteit Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands
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Marcel Swart;
Marcel Swart
Theoretical Chemistry, Materials Science Centre, Rijksuniversiteit Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands
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Ferdinand Grozema
Ferdinand Grozema
Theoretical Chemistry, Materials Science Centre, Rijksuniversiteit Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands
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J. Chem. Phys. 117, 8442–8453 (2002)
Article history
Received:
October 22 2001
Accepted:
August 13 2002
Citation
Piet Th. van Duijnen, Alex H. de Vries, Marcel Swart, Ferdinand Grozema; Polarizabilities in the condensed phase and the local fields problem: A direct reaction field formulation. J. Chem. Phys. 8 November 2002; 117 (18): 8442–8453. https://doi.org/10.1063/1.1512278
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