аЯрЁБс>ўџ 8:ўџџџ7џџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџьЅС#` №ПИ(bjbjmЅmЅ .0ЯЯkџџџџџџЄЄЄЄЄЄЄЄИ    Tє И:Ж     ччч‰‹‹‹‹‹‹$№hXVЏEЄчччччЏЄЄ  лєЭЭЭч2 Є Є ‰Эч‰ЭЭЄЄЭ  аЅшSxЬ pЭu 0:ЭЎ‰"ЎЭЎЄЭЈччЭчччччЏЏЋ"ччч:ччччИИИd„ИИИИИИЄЄЄЄЄЄџџџџ A Molecular Dynamics Study of the Specific Aspects of Counterion Condensation onto the Poly(styrene-sulfonate) Anion and Poly(allylammonium) Cation Gordan HORVAT & Josip PO}AR Laboratory of Physical Chemistry, Department of Chemistry, Faculty of Science, the University of Zagreb, Horvatovac 102a, 10000 Zagreb, Croatia. The phenomena of counterion condensation onto the synthetic linear polyelectrolytes of high charge density in solution is known for decades. However, detailed understanding of the influence that structure, charge, and charge density of counterions have on their distribution within the polyion domene is still rather limited. In order to gain a deeper insight into the abovementioned aspects of ion condensation we have performed explicit solvent all-atom molecular dynamics simulations of two systems containing studied polyions, namely poly(styrene-sulfonate) anion (PSS; Pn =100) and poly(allylammonium) cation (PAH; Pn =100), counterbalanced with various monovalent cations (M+; M = Na, K, Cs,) and anions (A-№; A= F, Cl, Br, I, NO3, ClO4) in TIP4P water. Polymer chain parameters were based on OPLS-AA forcefield. Gromacs 4.5.3 package was used to perform the simulations. The choice of counterions was based on their notably different charge density and, in some cases, structure (NO3-№, ClO4-№). In the case of PAH energetically most favorable condensation was obtained in the case of NO3-№ № №with whom the polyion has the most direct contacts. Also, the notably favorable condesation of perchlorate anion was observed.DFVXln‚„ЎАорђє  ( D H T V b C D E F W i o ‰ Б М Р їђїђїђїђїђїђцнцнцнцбТбТбЗЏЄœrch`ghъ4ЖCJaJmHsHh`ghb;ѕCJaJmHsHh`gh‹GШCJaJmHsHh™CJaJmHsHhm"mHsHhУTBhУTBCJaJhm"CJaJhцg‚hm"CJaJh9nthm"CJaJmHsHhm"CJaJmHsHhz85mHsHhm"hm"5mHsH hz85hm"hm"5#( * b D E Œ Dм%Š'Ж(И(єььффййЮУЮЮ $dha$gd + $dha$gd#|ƒ $dha$gd$>p$a$gdУTB$a$gdm" $dha$gdm" И(ўР Ц г м ф і  ' > C X Y r s u { ƒ Š ‹ Œ  єхжЧжЛЏ ‘ Џ ‚ v‚g XL= h`gh5яCJaJmHsHhцO™CJaJmHsHh`gh˜?XCJaJmHsHh`ghдZCJaJmHsHhУ5нCJaJmHsHh`gh!8ЎCJaJmHsHh`ghъ4ЖCJaJmHsHh`ghb;ѕCJaJmHsHh™CJaJmHsHh Z™CJaJmHsHh`ghŒ5†CJaJmHsHh`gh№3CJaJmHsHh`gh‹GШCJaJmHsHhЫ ШCJaJmHsH И Н Ц Ч у ч ѕ    " , - 1 5 H a  ƒ … ёхжЪЛёЌŽёpёaёRCh`gh_TCJaJmHsHh`gh%yCJaJmHsHh`gh`#CJaJmHsHh`gh7ЧCJaJmHsHh`gh5яCJaJmHsHh`ghuКCJaJmHsHh`ghФrЗCJaJmHsHh`ghEsљCJaJmHsHh`ghІECJaJmHsHhZpcCJaJmHsHh`ghb;ѕCJaJmHsHhƒXBCJaJmHsHh`ghNCJaJmHsH… † ‡ ˆ Œ  Ž ’ Ќ Б Г Д Е Ж К Л М б л я № џ  ,янЭОЏОЃ”ЏОянЭОЏ…Ѓ”vfv…ЃvRv'h`gh5яCJH*OJQJaJmHsHh`gh5яCJH*aJmHsHh`gh5яCJaJmHsHh`gh`#CJaJmHsHh`ghNCJaJmHsHh›3xCJaJmHsHh`gh%yCJaJmHsHh`gh_TCJaJmHsHh`gh_TCJH*aJmHsH"h`gh_T6CJH*aJmHsHh`gh_T6CJaJmHsH,.8:DZ\^Ќад0FJdfЄІЌфью ярярбрбТбЖЇ›Тб€q€b›SGShC2CJaJmHsHh`ghУTBCJaJmHsHh`ghъ4ЖCJaJmHsHh`ghЩa…CJaJmHsHh`ghcE^CJaJmHsHh…1ZCJaJmHsHhѕ CJaJmHsHh`ghѕ CJaJmHsHh5kPCJaJmHsHh`gh_TCJaJmHsHh`ghU.nCJaJmHsHh`gh5яCJaJmHsHh`gh5яCJH*aJmHsH (*,68:<@BDjlЄМјќўётвОтвОЏт ‘‚sgXgXH4'h`ghфHmCJH*OJQJaJmHsHh`ghфHmCJH*aJmHsHh`ghфHmCJaJmHsHhR<РCJaJmHsHh`gh%yCJaJmHsHh`ghњaЃCJaJmHsHh`ghNCJaJmHsHh`ghg?їCJaJmHsHh`ghъ4ЖCJaJmHsH'h`ghУTBCJH*OJQJaJmHsHh`ghcE^CJH*aJmHsHh`ghcE^CJaJmHsHh`ghФ“CJaJmHsHlz$$$ $$$&$($.$0$>$@$B$J$L$N$Z$эсвЦКИКЉš‹{‹šgšg[šL@šhGДCJaJmHsHh`gh_TCJaJmHsHhбY?CJaJmHsH'h`gh#|ƒCJH*OJQJaJmHsHh`ghX!?CJH*aJmHsHh`ghX!?CJaJmHsHh`gh#|ƒCJaJmHsHh`ghУTBCJaJmHsHUh7eЌCJaJmHsHhо=5CJaJmHsHh`ghфHmCJaJmHsHhR<РCJaJmHsH$h`ghфHmCJOJQJaJmHsH The results for F , Cl-№ and Br-№ were similar, both in terms of energetics and distribution around the PAH chain. These ions showed less affinitiy for PAH chain than NO3 and ClO4 . The condensation of bulky I-№ № was the least favorable. The notable influence of cation charge density and structure on their distribution near the PSS chain was not observed. Moreover, the energetics of counterion condensation was similar for all investigated cations. The large differences in energetics of counterion condensation among PAH and PSS can be attributed to differences in side-chain rigidity and lenght. 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