title: Polarizability rescaling and atom-based Thole scaling in the CHARMM Drude polarizable force field for ethers.
abstract: Within the CHARMM polarizable force field based on the classical Drude oscillator, atomic polarizabilities are derived via fitting to ab initio calculated data on isolated gas phase molecules, with an empirical scaling factor applied to account for differences between the gas and condensed phases. In the development of polarizable models for the ethers, a polarizability scaling factor of 0.7 was previously applied [Vorobyov et al. J Comput Chem 3:1120-1133, 2007]. While the resulting force field models gave good agreement with a variety of experimental data, they systematically underestimated the liquid phase dielectric constants. Here, a new CHARMM polarizable model is developed for the ethers, employing a polarizability scaling factor of 0.85 and including atom-based Thole scale factors recently introduced into the CHARMM Drude polarizable force field [Harder et al. J Phys Chem B 112:3509-3521, 2008]. The new model offers a significant improvement in the reproduction of liquid phase dielectric constants, while maintaining the good agreement of the previous model with all other experimental and quantum mechanical data, highlighting the sensitivity of liquid phase properties to the choice of atomic polarizability parameters.
authors.affiliation: Department of Pharmaceutical Sciences, University of Maryland, Baltimore, MD 21201, USA.
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Baker
authors.forename: Alexander D
authors.initials: AD
authors.lastname: Mackerell
mesh_terms: D004560:Electricity; D004987:Ethers / Q000737:chemistry*; D005663:Furans / Q000737:chemistry; D005740:Gases / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D012996:Solutions; D012997:Solvents / Q000737:chemistry; D013816:Thermodynamics; D014835:Volatilization
chemical_list: D004987:Ethers; D005663:Furans; D005740:Gases; D012996:Solutions; D012997:Solvents
references.citation: J Chem Theory Comput. 2005 Nov;1(6):1133-52
references.pmid: 26631657
references.citation: J Chem Theory Comput. 2006 Nov;2(6):1587-97
references.pmid: 26627029
references.citation: J Chem Theory Comput. 2007 May;3(3):1120-33
references.pmid: 26627431
references.citation: J Comput Chem. 2009 Jul 30;30(10):1545-614
references.pmid: 19444816
references.citation: J Phys Chem B. 2008 Mar 20;112(11):3509-21
references.pmid: 18302362
references.citation: J Comput Chem. 2002 Nov 30;23(15):1466-71
references.pmid: 12370948
references.citation: J Phys Chem B. 2005 Oct 13;109(40):18988-99
references.pmid: 16853445
references.citation: J Phys Chem A. 2008 Jul 31;112(30):6992-8
references.pmid: 18593142
references.citation: J Chem Theory Comput. 2005 Jan;1(1):153-68
references.pmid: 26641126
references.citation: J Comput Chem. 2009 Sep;30(12):1821-38
references.pmid: 19090564
references.citation: J Phys Chem B. 2008 Jul 17;112(28):8298-310
references.pmid: 18570394
references.citation: J Phys Chem B. 2008 May 15;112(19):6233-40
references.pmid: 18198859
references.citation: J Chem Theory Comput. 2007;3(6):1927-1946
references.pmid: 18802495
references.citation: J Comput Chem. 2004 Oct;25(13):1584-604
references.pmid: 15264253
references.citation: J Phys Chem B. 2005 Apr 14;109(14):6705-13
references.pmid: 16851754
references.citation: J Chem Theory Comput. 2006 Jan;2(1):128-39
references.pmid: 26626387
references.citation: J Chem Phys. 2020 Sep 21;153(11):114108
references.pmid: 32962358
references.citation: J Chem Phys. 2004 Jun 1;120(21):9903-6
references.pmid: 15268007