Review of Polarography, Vol.64, No.

2, (2018)

Ȇȴ
Ǵ…âNJȬǷ,<?ɶơÚěǐɺƒåŐXv{€„X|‚-ȋģ
ēȼ Ğ a*

A Study of Electrochemical Interface and Reaction Simulations Using Density Functional Theory
Calculations
Minoru Otania*

Received September 17, 2018: Accepted after Peer-Review September 21, 2018

An electrochemical reaction at an interface between electrode and electrolyte is one of the central problems
in electrochemistry. The history of theoretical and computational approaches devoted to this problem has
been reviewed. We paid particular attention to the detail of a series of simulation technique based on the
effective screening medium method, which is a core part of the comprehensive simulation platform for
electrochemical reactions. The simulation platform enables us to understand and clarify the detail of the
reactions quantitatively.

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–––––––––––––––––––––––––––––––––––––
a
ǍƑŢȟȆîǠǯşƘȎƇŴT‚m{c„X
|gdWG‚Ǡǯ[‚^„ʉ 305-8568 Ș
ĉǙ%/ijƏĂ 1-1-1ʊ
Research Center for Computational Design of ÿʍ
ɶơÚěǐɺ)ǐɺœɌ-ɸɶuc‚
Advanced Functional Materials (CD-FMat),
Xzʉ𝑉𝑉ʊ-Ɣőÿ𝑉𝑉" , 𝐸𝐸.@ @Ƶƭj
National Institute of Advanced Industrial Sciende
and Technology (AIST), 1-1-1 Umezono, Tsukuba PɿĊ-ɸɶuc‚Xzɶƒɶ¥CǤ
City 305-8568, Japan. 𝑧𝑧ɆCȡɺĆǗŶð𝑥𝑥𝑥𝑥ŶðCȡɺƢķŶð
*E-mail: minoru.otani@aist.go.jp. ,æ$'?

79 
Review of Polarography, Vol.64, No.2, (2018)

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80 
 Review of Polarography, Vol.64, No.2, (2018)

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81 
Review of Polarography, Vol.64, No.2, (2018)

 - Ŷ ƨ ( . Ƣ ǽ Ǔ nj å Ő ʉ hydrogen
evolution reaction: HERʊ-ǽɗǩ,'
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O„. Pt -𝜇𝜇e <>ʇ!9,ÿ 3(a)-İ (ŝ.ɶƒȡɺķȞŶðʉ𝑥𝑥𝑥𝑥Ŷðʊ, 2
ð-ǟà-Ŷð,ɶĘǨØȒǓǔ,Ɂ ƙ¼ PBC CȵzŶð2.¡Ř-čǐƈ 

82 
 Review of Polarography, Vol.64, No.2, (2018)

C ȵ  Ư î č ǐ ƈ   ʉ mixed boundary F‚V‚oƨ(? Andersen -ăԅĝ

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OBCʊ)!Čî-Q~„‚ɬű. i
4𝜋𝜋 Sc |dSde| + 𝜇𝜇e 𝑛𝑛e
𝐺𝐺 OBC (𝒈𝒈∥ , 𝑧𝑧, 𝑧𝑧′) = e ∥ (5) )+?(𝑀𝑀i <0𝑹𝑹𝒊𝒊 .@ @â
2𝒈𝒈∥
Ę-ɀɤ<0ļƗ(?6!𝑊𝑊.Ÿŗ
)ȡ@?(𝒈𝒈∥ . 2 ƙ¼ɏǰɫrP
ǔ+ɶȚ-ɀɤ(?ľ(6)-LG}„-}
e(?ȡɺƒǐɺ(<ǎ=@?
Q}‚Y{Ŷǩľ.
- MBC ,<?ɬű-ľ(5)-< +ȡǤŶƨ
𝜕𝜕𝜕𝜕({𝑹𝑹𝒊𝒊 })
C Laue ȡǤ) Ÿę- DFT pQ}w 𝑀𝑀 𝑅𝑅̈ = −
t i i 𝜕𝜕𝑹𝑹𝒊𝒊 (7)
, ESM ƨCĦÀ?-.ƞɈǔǺÞ(?
𝑊𝑊e 𝑛𝑛ë = −(𝜇𝜇int − 𝜇𝜇{ )
ESM ƨ.ɸɶuc‚Xz2±ƚCÖ?
)+?(𝜇𝜇int . Janak -ĝNJ=ȬǷ
:-(>Ɓ:ȬǷżɫ-? SCF Ȭ
@??ǝɫ-ɶĘ-RvMuc‚X
Ƿ-ɟÉ,.ŠCÀ@?ŏȤ+6!
z(>𝜇𝜇{ .^„Sae)+?RvM
Q~„‚ɬű‘9É$'?-(uF
uc‚Xz(?𝑛𝑛e .(𝜇𝜇int − 𝜇𝜇T ) CŌ¼
a]‚ŶǩľCpQ}wŒ(ȩŏȤ
Ô)'𝜇𝜇T -ó>CŧØ?6!ľ(7)-
+ʼn$'3D-PBC CȵɑĶ- DFT Ȭ
©ÑɶȚ,?ÔCǎ'ƁɛÚùʁC
Ƿ)4)D*ïǩĻ-ȬǷȾȚ(ɶơÚě
ȩ)ɶƒɶ¥C^„Saeɶ¥ʉ𝜇𝜇T /𝑒𝑒ʊ
ǐɺXv{€„X|‚éȎ(?
)?< ,©ÑɶȚCƁɛÚ?)

ESM ƨCǎ?),<>ÿ 3(b)-<
(?constant-𝜇𝜇e ƨ,<$'ȵʁ 2 CȩƦ
+ɶƥǼCyd~‚Q?)éȎ)
?)(!ƅŠƨ-ɛǎ¬)'.
+?-Čî.Ĥƒ, ESMʉϵ = ∞ʊCȉ
OER - cyclic voltammetryʉCVʊ-Xv{€
'?ÿ 3(b)-< , Pt ,©ÑɶȚC
„X|‚ 18)Ŧ=@?constant-𝜇𝜇e ƨCǎ
À@?)ESM ‡,.@CɜȜ?ɶȚ
' OER -åŐǽɗǩ-ƪŔÚJiO„
ȒØǔ,ĦÀ@?-(‹ƒɫ,.Ÿŗ
CȬǷɒĻȷ)ȁ7îB'Ğʆ(Ŋ=
ǔ+ɶƥŪȄ@!-)Ƕ®,+>©Ñ
@'? CV )ĝŔǔ,…Ȕ?ȂƌCŊ?
ɶȚCÎŋ?),<>ɶăCàÖ?
)(!
)éȎ,+?@(ȵʁ 1 ȩƦ@
Ğɲ,ÿ 3(b)-ydCǎ'HT OQ =
ʏʌʏʌƜ@!ùʁ
Ƣǽ Pt ȡɺ,òǜ?åŐ-Xv{€„
X|‚,Ë9'ŜÕ! 16)ïƖ-ydC
ȵʁ 12 ȩƦ@!),<>LjĞǔ
ǎ'Ē-Ǡǯ+@'? 38-41) +ɶơÚěǐɺXv{€„X|‚,ŠĪ
< ,+$!ɪǓɐ‡(ňú
ʏʌʎʌɶă…ĝ-Ŷƨʉconstant-𝜇𝜇e ƨʊ
,!ùʁ:Ĩ++ǃ,ȵʁ 3 Cȩ
ƦXv{€„X|‚Ţȟ-ĜŜĻ;Ƥǎ

ESM ƨCǎ?),<>ÿ 3(b)- Pt
ŔCʇ9?!9,.ˆ,Ǥ! a)
e)- 5
) ESM ‡-©ÑɶȚ,ǁNJǔŘôCŠ?
%-ùʁCȩƦ?ŏȤ?
)éȎ)+>‹ɶƒɫ-ɶ¥ıĝȊ
a) ES ,ĤGL‚ęĄ+
éȎ)+?-yd(ɑĶ- DFT ȬǷ
b) åŐǪ…%+!9,åŐ-Ð
CȞ ) ɶƒ‡- ©ÑɶȚ CĀĝ!
ň(ɶȩƭ-ƹĻÓǔ,ĐÚ?
constant-𝑛𝑛e (-ȬǷ)+?ÐɎ-< ,
c) ɶĘǨØ-e~aP.åŐǗÐ(
ɶơÚěǼ(. constant-𝜇𝜇e -ˆ(Xv{€
-7ƚ
„X|‚CȞ ŏȤ?ŝ.ŤŁǼ-

83 
Review of Polarography, Vol.64, No.2, (2018)

‚- GCE CĞLj?Ŷƨ.ęĄ+

c).[PX|‚ 3.1 (ÿ 3(a)Cǎ'ȩȴ
!e~aP-ùʁ(? Ȃƌǔ,
åŐǗÐ-ɶơÚěǐɺCÇLj'?
LjĞ-Ǽ(.Pt ‡-ɶȚ-ɁƳ.HT O=
-:-(.+uc‚X|Z^ae=Ħ
À@!©ÑɶȚ(-©ÑɶȚHT OQ
CƢŒ=Ŀġ!:.ƢŒ=
Ɍġ$!HT OQ  Pt ‡,ɨºɶȚCȲɁ!
:-(?Ɣőǔ+ùʁ(.?-
ə.ƙ-<
+ŒȋĞʆC?)yd
Ȓ§ǡȅ?’NJȩ(?ÿ 3(a)Œ-
ÿ 4
ES )LjĞ-ɶȩƭ-ə-Ɣőÿ(a)ES HT OQ Cÿ 4(a)-<
,ƢŒ-jPɿĊ6
(HT OQ CƵė-jPɿĊ,!Čî(b) (Ŀ$Ł$'Ȟ$!żCȋ?ĤGL‚
LjĞ-ɶȩƭjPɿĊ-HT O ,Ʃǖ!Č Q ęĄ+-(HT OQ -ó>,FhL‚C
î(b)(.ĤGL‚HT OQ )j}‚Z?! ñ8GL‚ɵþơńŜ@jPɿĊ
9Pt ‡,©ÑɶȚ.ęĄ+ ,':iae,+1®-ɶȚCť#
¼Ȓ=°ť'!−1®-ɶȚ. Pt ‡
d) ƂƘƵė+*Ƣ<>ē+ƵėÉĘ ,ęĄȄ?-ūº.ź=,ȳ>(
Cǎ?)ȬǷȾȚÓǔ,ĎÖ? >LjĞǼ(.jPɶȩƭŒ-HT OQ -
e) ES Cǎ'?ɮ>š?Ǽ-Îɮ ó>,.ÿ 4(b)-<
,GL‚ɵþơń
.ēƹĻCĐ!>ƯîƵė Ŝ@iae,ɶȚ.ť!+!9,Pt
+*Cš
).ýɴ :ŒŔ(?ÿ 3(a))ÿ 4(a).ÁïNj

6ƮÏĻ-ʇ a)Cȥ?ÿ 3(b)-yd č(HT OQ -ęĄ?¥ȉ,<$'yd
Q
ċƅ)+?ɶƒœɌ,HT O -7 ǡȅ!>+$!>?-.ź=
ęĄ'>ĤGL‚-ClS Ƕ.ęĄ+ ,ydȒ§,‰¶?‡Ɏ-ȴź(.
ɶƒCȾ,ĵɶ'?-(FhL‚ Řÿǔ,ƢŒ)ɶȩƭŒCÛÌ'
.ɶƒ=ɳ@?¸ð,>ɶƒ= 10Å «$!Ȃĩ-)A a)-ĤGL‚%6
ǩĻ-ş,.FhL‚+':ùʁ+ >ɶȩɀGL‚Ǽ,ęĄ+)
ù
-(.+)ƓȨǔ,ȋ?):é ʁ,Ȟǜ
Ȏ(?ųdž 32 - IS )-ǐɺC7?)
6(ȥ'! a)
c)-ùʁ.3.1 (
ÁęĄ+)
).+6! ĦÀ! ESMʉϵ = ∞ʊCĤƒ)'ȋ
::ĤGL‚+) EDL .ĜȂ+ ǼCÿ 3(b)-<
,Áɶƥ)Ũ!’(ƫ
-(¬/ÿ 3(b)-yd(.©Ñɶ 0‡?ùʁ(?@.ȋ
ȚÉ.Ƣ-ɿĊ(.ĜÁ,ɜȜ@'+ Ŷ-ùʁ(>ÿ 3(b)-ë´- ESM .Ĥ
ʼn$'jPɿĊ(:ɸɶuc‚Xz ƒ(.Ƽȵʁ 34 CȩƦ?!9, EDL
.Ƃɮ-¸Cť$'6
-(ɶƒɶ CydÚ?!9,ĦÀ@!Ǵ 0 Ɍ¤
¥CƦ9?’ɴ+? ǔ+Ƃ×ėɀ(?)NJȩ?):(

b)-ùʁ.DFT-MD (.Xv{€„X| ?-<
,ȋ?)a)
c)-ùʁ.Á
‚Œ,âĘűĐÚ+)=?ù
+
ʁ(?åŐǪåŐ'ǐɺœɌ=
)é
Ƭƶ':jPɿĊ=Ȣ½@?)
' ESM -Œ,ţɋ6@'ÿ 1 -<
Ýɶƥ-Xv{€„X|‚CȞ
Ȏ)+$!)ȋ?):(?:#AD
.+LjĞ-Ǽ(.jPɿĊ~W„j -șɌ¤-!9, EDL -ƕɓ;ɶƒɶ
„)+?-(ǐɺ(åŐǪƬƶ': ¥+*ȵʁ 34 ,ɬ?ȸùʁ-ĝɤŔ.
GL‚-RvMuc‚Xz,Ő'j DŽǂ)+$'?-(=+?ɪǓŏȤ
PɿĊ=ǐɺ2)åŐǪȢ½@? (?),.ĐB>+
@CȩƦ?,.GL‚,ɬ' grand
d)<0 e),ɬ'.Ǽ-Á'C DFT (
canonical ensembleʉGCEʊCĞLj?ŏȤ š$'?)-Ľğ(? DFT .ċƅǔ
?LjDž- DFT-MD (.âʃGL ,Ǽ-ɶĘű- 3 Ž(ȬǷɤĎē?-

84 
 Review of Polarography, Vol.64, No.2, (2018)

(¦ƹĻ-ɶȩƭƯîƵėƂƘƵė+ -< , Laue ȡǤ?),<>MBC -

*CȬǷ< )?)ȑē+ȬǷżɫC ˆ( RISM CÍǎ?)éȎ)+?
Ȥ?Ğɲ,Propylene carbonate (PC)CƵ -ČîȬǷ?yd.ÿ 2(d)-İ´-ɥ
ė)?~`HwGL‚ɶƥ- ES Cǎ! Ĭ-=,İ´,.ǚǰĹ>ë´- IS
Xv{€„X|‚(.…ú-ȏƵėöɗǩ ɿĊ.Ƽɮɚ6( IS ȄjPɿĊ)+
,–T‚m{„^Cǎ' 2 ĸǩĻ-ȬǷ ?@(ŃË;>!$!ÿ 1 -Ýɶƥ
żɫCȤ! 19) -Xv{€„X|‚éȎ,+$!

- ESM ƨ) RISM ȝî!ŶƨC
ʏʌʐʌESM ƨ) RISM -ȝî ESM-RISM 32))õ1ESM-RISM (.+𝑧𝑧Ŷð
.ɶȩƭ-jPɿĊ2)Ȓƽ,%+?

‡Ɏ- a)
e)-ùʁ.ɶȩƭC ES -7( !9,GL‚,Ĥ' GCE ĞLj
š )!),<?:-(? Njč constant-𝜇𝜇ion ˆ(-ȬǷéȎ)+?6!
)'š?ɶȩƭ-ɟÉ.ȬǷȾȚ-ɢ ÐɎ-< , RISM (. ES ) RISM - hybrid
 ES (.ƼȬǷȾȚ-ɇ IS CĦÀ CȞ ɲ, cavity Cǰ?ŏȤ+ƺ:
'èÅǔ,š$':ȗ6!ɶơÚěǐ ē+x~ae(?=,ÉĘūºC
ɺXv{€„X|‚(.Ƶė;ɶȩɀGL °ť'?!9,Ƣžđ-ƂƘƵėǶ:
‚-~W„j„)'-jPɿĊŏȤ Ȓƽ,š )(ƯîƵė:š )
(>GL‚-RvMuc‚Xzʉ𝜇𝜇ion ʊ éȎ(?%6>ÐɎ-ȵʁ 3 ȩƦ-
C…ĝ,°%)(? GCE )ȧöŔ- !9-ùʁ a)~e)ESM-RISM ƨCǎ?
ȗ IS Cɝ1ŏȤ?ŝ.-< ),<$'…ơ,ȩƦ@!),+?
+ IS )' RISM CɝD"

RISM ) DFT - hybrid ȬǷ.ɑĶ-Āƭ ʏʌʑʌɶƒɶ¥-ƦĝŶƨ
ǐɺ,.ɛǎ 9)@'?ɶơÚěǐɺ
2-ɛǎ¬.+$!ȶ3'7?)RISM
<<ȵʁ 4 (?ɶƒɶ¥-âƺC
. GCE CÈǓƺ)'?-(ŝ-Ȥƣ Ʀ9'Ğʆ)ƞɈéȎ+ɶ¥-ƦĝŶƨC
,Ő?)(?3D-RISM-SCF ( ǢDz!@.ɶơÚěXv{€„X|
. RISM Ŷǩľ ‚Ţȟ-Œ(.Ɓň,Ɯ@!ȍƊ-<
+:-(Ā§ǁNJě-ǠǯȌ,)$'Ɓ:
ℎ; (𝒓𝒓) = g € d𝒓𝒓′𝑐𝑐: (𝒓𝒓e )𝜒𝜒:; (𝒓𝒓e − 𝒓𝒓) (8) É>,:-(?ɶƒɶ¥)ɥĬŒ
:
C†ƙ¼ʇɒn„~JĐŭʉ3D-FFTʊ(ǒ7 -ɶĘ-𝜇𝜇e .¨=-ń(ɬ¯?).
ɋ7ǭÉCǎ'ȬǷ'?)É Ǘřǔ,.ɫə+)ŒB@?DFT Ȭ
$!(ℎ, 𝑐𝑐, 𝜒𝜒.@ @Áǘɬɬű Ƿ(È'?𝜇𝜇e )ɶƒɶ¥¬/ SHE 
ǗŪǘɬɬű<0ƵėřçLJ(>𝛼𝛼, =-ɶ¥𝐸𝐸[SHE]-ɬ¯NJȩ(+ɶơ
𝛾𝛾.âĘVGe(?3D-FFT CȞ ) Úě-Űǧſ,<?)ƗƴDžŚCȋ!Č
).Ǽ, 3D-PBC Cȵ'?))Ƕ î,Ɨƴɶƒɶ¥).åŐ,ĀƂ-ɤ(
®(>-66(.ɶơÚěǐɺ2.ɛ >ɶƒ-ɥĬǪ,.ġ=+)@'?
43)
ǎ(+-’Ğ,ơœ!ż, ŝŽƝȬǷ?ɥĬ/ǚǰǐ
,ɑĶ- DFT ,':ïNJǏ(ɶơÚ ɺ(.ɥĬǪ,<$': ɺŶ¥,<$':
ěǐɺǼ2ɛǎ(+ʉľ(3)(4)ãƾʊ) ǚǰ=Ʊ$!𝜇𝜇 e %6>š’ɬű.Ǒ+?
)-ʂ¤Ŕ,ơœ!ʼn$'RISM , -(ɥĬǪ,ġ=+) Ł.ǗȨǔ
':ľ(2)-1/𝑟𝑟C ESM ƨ(ȬǷ! OBC ,NJȩ&=ȵʁ 3 6(ȩƦ
-Q~„‚ɬűʉľ(5)ʊ(ȉŭ?), !),<>ŝ.łÔ+Xv{€„X|
<>ɶơÚěǐɺǼ2ɛǎ(?)É ‚b„CŠ,À@'>ȯȞɧȳCȈ>
$! ɍ  +  = ɶ ƒ ɶ ¥ - Ȭ Ƿ Ŷ ƨ C ESM-

ħǔ,. RISM Ŷǩľʉľ(8)ʊC RISM -ǸþÆ(ǢDz?)(! 36)
ℎ; (𝒈𝒈∥ , 𝑧𝑧)
"
= g € d𝑧𝑧′𝑐𝑐: (𝒈𝒈∥ , 𝑧𝑧′)𝜒𝜒:; (𝒈𝒈∥ , 𝑧𝑧 e − 𝑧𝑧) (9)
: S"

85 
Review of Polarography, Vol.64, No.2, (2018)

ÿ 5
ǚǰ/ɥĬ/ɶȩƭ/ǚǰ-ɸɶuc‚Xz
pnEG-Ɣőÿƺȇ.ɥĬ-nI
vJiO„ʉ𝜀𝜀f ʊȡųdž 36)ÿ 6 C±ƚ

ȵʁ 4 ,æ>ȁ8,.Trasatti - SHE , ÿ 6
(a) Pt+H5 O<0(b) Pt+HT OQ -ǐɺy

Ĥ?ȃĤɶƒɶ¥-ȋŶ 44)ċƅ)+
?Trasatti .ǚǰƴ¥-ĝȊ,«
ɥĬɌ
µ-ǚǰʉΦVM ; ÿ 5 İ´ʊ)ïƖ,SHE -
âƺ)+?ǚǰCȮĝ!@.ÿ 5 -
dǚǰŒ<0 RISM Œ-ĚDz!(c) H5
(d) H5 O <0(f) HT OQ -yd(f)Pt/RISM -
ǐɺydRISM .(a)(b)(f)(.ë´(d)(e)
(.‹´ constant-𝜇𝜇ion -jPɿĊ,@
ë´-ǚǰƴ¥ʉΦVS ʊ(>ɶȩƭ- @ŪȄ'?
/-ǚǰ(?Câƺ)æ?), ȎŔ?)CǤ÷'?Ğʆ(.
<> ƿÔěǔ,ƣ9!ķȠɶ¥ ΦS .ȨƱéȎɤ(+)=Ãɑ-â
(Δat 𝐺𝐺 ∘ + Δion 𝐺𝐺 ∘ + 𝛼𝛼H∘,Sè )/𝐹𝐹 = 4.44 V (10) ƺ,.ũǎ@'+RISM Cǎ?
)ƢɦɶƒCǎ'ƢǽǓnj-ķȠDžŚC Čî.ΦS . well defined +ǁNJɤ(?
ª$'Ʊĝ'Ŋ=@?ɶơÚěǔ, )=âƺ,ũǎ(?éȎŔ?ù
ƣ9!ķȠɶ¥ ʁ.ΦS Câƺ)'ľ(10)(11)-ɬ¯Ʋ!
ΦVM /𝑒𝑒 + ΔM M
S 𝜓𝜓 − 𝐸𝐸S (𝜎𝜎 = 0)[SHE] @?(?ESM-RISM Cǎ@/…
(11)
= 4.44 V Ȕ?)CǤ)(?ȱǾ.ųdž
…Ȕ?)Ǥ@-³ȃĤɶƒ 36)Cãƾ'ɼ!ƅǬ(:ǺÞ,
ɶ¥𝐸𝐸(H Q /H)[abs])ĝȊ@!( ľ(10)(11)-ɬ¯Ŝ>Dz%M}P~Cȴź
Δat 𝐺𝐺 ∘ Δion 𝐺𝐺 ∘ <0𝛼𝛼H∘,Sè .@ @Ɨƴ ?-ΦS Cċƴ,ǎ?ŶƨC inner
DžŚ,?Ƣǽ-âĘÚJiO„GL potential ƨ)õ1
‚ÚJiO„<0H Q -ƵėöȒǏJ
SHE -åŐľ.
iO„(?6!ΔM M
S 𝜓𝜓 <0𝐸𝐸S (𝜎𝜎 = 1/2H5 (gas) + H5 O(S)
(12)
0)[SHE].@ @t^ɶ¥ı<0 ↔ HT OQ (S) + 𝑒𝑒 S (M)
SHE =- potential of zero chargeʉpzcʊ-ɶ )+?(gasS<0M.@
¥ı(?2 %-Ǒ+?Ŷƨ(ȬǷ@! @ƗƴDžŚ-ơǘŒɶȩƭŒ<0ɥ
ķȠɶ¥…Ȕ!)
).ΦVS Cà Ĭ Œ -Dž ŚC ȡ  ESM-RISM ,  ?
ɑ-âƺ,æ@?)
)(?%6> Helmholtz free energy 𝐴𝐴<0 Grand potential
ɥĬ,­ę+ɡÚɞ¼ɶ¥ʉľ(10)ʊ Ω.
)…Ȕ?𝜇𝜇e /𝑒𝑒CĞʆCȞ
ɶƒ(:Ȯĝ 𝐴𝐴 = 𝐸𝐸DFT + Δ𝐴𝐴RISM + 𝐸𝐸ZP (13)
(@/ʉľ(11)ʊ - SHE -RvMu Ω = 𝐴𝐴 − 𝜇𝜇e Δne (14)
c‚Xzʉ𝜇𝜇eSHE ʊ=-ıȃĤɶƒɶ )ȡ@?(𝐸𝐸DFT Δ𝐴𝐴RISM 𝐸𝐸ZP
¥Cċƴ)!ɶ¥𝐸𝐸[SHE] = −(𝜇𝜇e − 𝜇𝜇eSHE )/ <0Δne .@ @DFT -ÁJiO„
𝑒𝑒(?)
)(?@NJȩ( RISM -ȒǏJiO„\ƺŧØ-Ji
@/𝜇𝜇e )𝐸𝐸[SHE]Cɬ¯œ=@?ù O„©ÑɶȚCȡ𝐸𝐸ZP.Ā§-Čî.
ʁ.ΦVS =𝜇𝜇e CƱ?ȟ+)(? ġŠħ)' 0 )'?
ŝš$'?-. 3.4 (ȴź!<
+
6ľ(10),ǘŃ?ɤCȬǷ?å
Ýɶƥ-yd+-(Ƶƭ-đ-ǚǰ Ő ľ (12) - İ Ɋ  < 0 ë Ɋ - Gibbs free
%6>ΦVS .ęĄ+ energy C@ @

Trasatti .ΦVS -›,:ÿ 5 -ɶȩƭ-j 1
𝐺𝐺L = 𝐴𝐴(H5 , gas) + 𝐴𝐴(Pt+H5 O, RISM) (15)
P ɿĊ -ɸɶ uc‚ Xz ( ? inner 2
potentialʉΦS ʊCÃɑ-âƺ)'š?é 𝐺𝐺R = 𝐴𝐴(Pt+HT OQ , RISM) (16)
)ĝȊ?(RISM .ƗƴDžŚʉ1M

86 
 Review of Polarography, Vol.64, No.2, (2018)

'?)É?

6(NJȩ!Ɲɱ(ΔGSHE .åŐĀ
Ƃ-ɤ+-(ÿ 6(a)(b)-Ɩ+ɠȉ<>:
8Aÿ 6(d)(e)-Ɩ,ȬǷ!ŶǽǗ(
?),ơœ!Ğɲ,
1
𝐺𝐺L = 𝐴𝐴(H5 , gas) + 𝐴𝐴(H5 O, RISM) (21)
2
Q
𝐺𝐺R = 𝐴𝐴(HT O , RISM) (22)
-Ɩ,ĝȊ'ÿ 6(c)-(e)-ȬǷC?)
𝜇𝜇eSHE = −5.23 eV)+?ľ(15))(16)(ȬǷ
!³)0.04 eVı?@.ÿ 6(a)(b)-
ȬǷ(. Pt )H5 O<0HT OQ -ǘ”ªǎ
6"Ɯ$'>ÜÉ,ɳ'+$!
),<?J}„(ĚDzǼCȬǷ'?ľ
(21)(22)ǻĻ-ʇȬǷ)+$'?ľ
ÿ 7 (a) Pt<0(b) Al ,Ĥ? Grand potential
ΩL , ΩR-paeÈÅ.ųdž 36)ÿ 5 (18)(19),ɬ':
1
ΩL = 𝐴𝐴(H5 , gas) + 𝐴𝐴(H5 O, RISM)
HCl aq., T=298.15Kʊ(íɾ.ÿ 6(a)-(c)- 2 (23)
+ Ω(Pt, RISM)
<
+ɠȉ(ȬǷ'?ÿ 6 (a)(b)(.
ΩR = 𝐴𝐴(HT OQ , RISM) + Ω(Pt, RISM) (24)
Pt )H5 O/HT OQ .ÜÉǘ”ªǎŀ+?<
-Ɩ,ĝȊ' ÿ 6(c)-(f)Cǎ?)ÿ 7 -

,10Å ɳ'?6!𝐴𝐴)𝐺𝐺-ə(
Ȃƌ.𝜇𝜇eSHE = −5.23 eV)+>T‚XZc‚
?ăÔקǭ-ɾ.ñD(+ΦS Cċ
e+Ȃƌ)+?
ƴ)ƿÔěǔ,ƣ9=@!ɶƒɶ¥.

ÿ 6(a)(b)Cÿ 6(c)-(e))Éȩ?Ŷƨ.Ȭ
ΔGSHE = −( 𝐺𝐺L − 𝐺𝐺R ))'
ǷȾȚ-ɺ(:»@'?(a)(b)(.‡Ɏ
𝐸𝐸(H Q /H)[vs. ΦS ] = −ΔGSHE /𝐹𝐹
)ȡ=@ ?˜ú -ƈ ( -ȬǷ³.
ΔGSHE = −5.27 eV($!

ƙ,ľ(11),ǘŃ?ɶƒɶ¥Cƣ9?
(17) -Ɩ,ƅƉæ>ɰ!.-ɶƒ)-ǘ
”ªǎJ}„)'ƯÀ?éȎŔ
?(c)-(e)(.J}„-ƯÀ.ɭ'
%ȬǷȾȚɹĶ,ɇȬǷ,ȉŭ=
Xv{€„X|‚(ɶơÚěǔķȠDžŚC @'?
ƣ9?!9,.åŐľ(12)-İɊëɊ-

Ɓň,+ΦS CÃɑ-ɸɶuc‚Xz
Grand potential ΩL ΩR C@ @ -âƺ)æ@!-Cȩȴ?ESM-
1
ΩL = 𝐴𝐴(H5 , gas) + Ω(Pt+H5 O, RISM) (18) RISM (. RISM Ŷǩľʉľ(9)ʊC OBC (
2
ȩ'?ʼn$'𝑧𝑧Ŷð. constant-𝜇𝜇ion -
ΩR = Ω(Pt+HT OQ , RISM) (19)
RISM ŪȄ'?jPɿĊ-ΦS .Ã
)ĝȊ?Ω.ľ(14)(ĝȊ@ÿ 6(a)(b)
ɑ+-(¬/ÿ 6(a)(b)(d)(e)(f)-ΦS .Ã
-yd(𝜇𝜇e CĐÚ+=ȬǷ?
ɑ)+?%6> OBC CĦÀ!)

ΩL ΩR .𝜇𝜇e -ɬű)'ÿ 7(a)-<
,+>
)ƅɀǔ,ɢȤ(?)É?
‹žȇ•ı?ż-𝜇𝜇e ķȠɶ¥𝜇𝜇eSHE (

@(ŝ.ɕ,ķȠɶ¥Cċƴ)!
?ʼn$'ɶơÚěǔɶƒɶ¥.
ɶƒɶ¥𝐸𝐸[SHE] = −(𝜇𝜇e − 𝜇𝜇eSHE )/𝑒𝑒ȬǷ(
𝐸𝐸(H Q /H)[vs. ΦS ] = 𝜇𝜇eSHE /𝑒𝑒 (20)
?Ɩ,+$!-ŕŖCç=@?-.
)ȡ@?˜ú-ƈ (-•ƺ-¥ȉ.ÿ
RISM CĦÀ'ɶȩƭ,­ę+
7(a)(Ǥ@?<
,𝜇𝜇eSHE = −5.27 eV(
ΦS CĝȊ?)(!=(?
$!@(ƿÔěǔ<0ɶơÚěǔ,
@(ȵʁ 4 :ȩƦ!
ƣ9!ķȠɶ¥…Ȕ?)Ǥ!-
(ΦS .ɶƒɶ¥-ċƴ)'-ȿƍ
ʐʌ6)9
?Pt žđ-ɥĬ¬/ Al ,ɬ':ï
Ɩ-ȬǷCȞ
)ÿ 7(b),Ǥ<
,
6(ȥ'!Ɩ,ESM ƨ 37)Cɂ
𝜇𝜇eSHE = −5.22 eV)+>ɥĬǪ,­ę >)'constant-𝜇𝜇e ƨ 34)ESM-RISM32)
ʉȬǷǻĻ-ǸþÆ(ʊåŐĀƂ-ɤ)+$

87 
Review of Polarography, Vol.64, No.2, (2018)

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