Energetic Effect of the Carboxylic Acid Functional ... - ACS Publications

Luísa M.P.F. Amaral†§, Victor M.F. Morais†‡, and Maria D.M.C. Ribeiro da Silva† ... Miguel A. García-Castro , Patricia Amador , Aarón ...
0 downloads 0 Views 910KB Size
Subscriber access provided by Oakland University Libraries

Article

Energetic Effect of the Carboxylic Acid Functional Group in Indole Derivatives Tânia M. T. Carvalho, Luisa M.P.F. Amaral, Victor M.F. Morais, and Maria D. M. C. Ribeiro da Silva J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.7b00275 • Publication Date (Web): 30 Mar 2017 Downloaded from http://pubs.acs.org on April 4, 2017

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

The Journal of Physical Chemistry A is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 27

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

(QHUJHWLF (IIHFW RI WKH &DUER[\OLF $FLG )XQFWLRQDO *URXS LQ ,QGROH 'HULYDWLYHV

7kQLD 0 7 &DUYDOKRD /XtVD 0 3 ) $PDUDOD ‚ 9LFWRU 0 ) 0RUDLVD E 0DULD ' 0 & 5LEHLUR GD 6LOYDD

D

&HQWUR GH ,QYHVWLJDomR HP 4XtPLFD 'HSDUWPHQW RI &KHPLVWU\ DQG %LRFKHPLVWU\ )DFXOW\ RI

6FLHQFH 8QLYHUVLW\ RI 3RUWR 5XD GR &DPSR $OHJUH E

3

3RUWR 3RUWXJDO

,QVWLWXWR GH &LrQFLDV %LRPpGLFDV $EHO 6DOD]DU ,&%$6 8QLYHUVLW\ RI 3RUWR 5XD GH -RUJH

9LWHUER )HUUHLUD

3RUWR 3RUWXJDO

BBBBBBBBBBBBBBBBBBBBBBBBBBBBBB &RUUHVSRQGLQJ DXWKRU PGVLOYD#IF XS SW 0 ' 0 & 5 6 ‚

3UHVHQW DGGUHVV 5(48,07( 'HSDUWPHQW RI &KHPLVWU\ DQG %LRFKHPLVWU\ )DFXOW\ RI

6FLHQFH 8QLYHUVLW\ RI 3RUWR 5XD GR &DPSR $OHJUH

3

ACS Paragon Plus Environment

3RUWR 3RUWXJDO

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 27

$EVWUDFW 7KH VWDQGDUG PRODU HQWKDOS\ RI IRUPDWLRQ LQ WKH JDVHRXV SKDVH DW 7

. ZDV

FDOFXODWHG E\ FRPELQLQJ IRU HDFK FRPSRXQG WKH VWDQGDUG PRODU HQWKDOS\ RI IRUPDWLRQ LQ WKH FU\VWDOOLQH SKDVH DQG WKH VWDQGDUG PRODU HQWKDOS\ RI VXEOLPDWLRQ \LHOGLQJ í N- PROí DQG í

N- PROí IRU LQGROH



FDUER[\OLF DFLG DQG



PHWK\OLQGROH

FDUER[\OLF DFLG UHVSHFWLYHO\ &RPSXWDWLRQDO VWXGLHV DW WKH * 03 FDUER[\OLF DFLG DQG

PHWK\OLQGROH

FRPSRVLWH OHYHO ZHUH FRQGXFWHG IRU LQGROH

FDUER[\OLF DFLG DV D FRPSOHPHQW RI WKH H[SHULPHQWDO

ZRUN DQG ZHUH DOVR H[WHQGHG WR WKH UHPDLQLQJ LVRPHUV LQGROH PHWK\OLQGROH

FDUER[\OLF DFLG

PHWK\OLQGROH

FDUER[\OLF DFLG

FDUER[\OLF DFLG DQG

PHWK\LQGROH

FDUER[\OLF DFLG LQ RUGHU WR SURYLGH UHOLDEOH HVWLPDWHV RI WKH FRUUHVSRQGLQJ WKHUPRFKHPLFDO SDUDPHWHUV 7KH DJUHHPHQW RI WKH HVWLPDWHV RI WKH VWDQGDUG JDV SKDVH HQWKDOS\ RI IRUPDWLRQ VR REWDLQHG LQGROH DFLG LQGROH “



FDUER[\OLF DFLG N- PROí

FDUER[\OLF DFLG N- PROí DQG



PHWK\OLQGROH “

PHWK\OLQGROH

N- PROí

N- PROí

PHWK\OLQGROH

FDUER[\OLF DFLG



PHWK\OLQGROH

FDUER[\OLF DFLG



FDUER[\OLF N- PROí

FDUER[\OLF DFLG N- PROí ZLWK WKH

DYDLODEOH H[SHULPHQWDO GDWD JLYHV XV DGGLWLRQDO FRQILGHQFH IRU WKH VLWXDWLRQV QRW VWXGLHG H[SHULPHQWDOO\ 7KH HQWKDOSLF HIIHFW UHVXOWLQJ IURP WKH HQWUDQFH RI WKH FDUER[\O JURXS LQWR WKH LQGROH ULQJ ZDV GLVFXVVHG DQG DQ HQWKDOSLF VWDELOL]DWLRQ ZDV IRXQG IRU LQGROHV DQG S\UUROHV GHULYDWLYHV ZKHQ FRPSDUHG ZLWK RWKHU VLPLODU V\VWHPV

î ACS Paragon Plus Environment

Page 3 of 27

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

,QWURGXFWLRQ 7KH LQGROH ULQJ LV DQ LPSRUWDQW FRQVWLWXHQW RI D KLJK QXPEHU RI FRPSRXQGV SUHVHQW LQ QDWXUH FKDUDFWHUL]HG E\ KDYLQJ D KLJK ELRORJLFDO DFWLYLW\

DQG WKHUHIRUH SOD\LQJ DQ LPSRUWDQW UROH LQ

WKH SKDUPDFHXWLFDO LQGXVWU\ 6HYHUDO VWXGLHV KDYH UHSRUWHG WKDW WKHVH FRPSRXQGV KDYH DQWLSUROLIHUDWLYH FDSDELOLWLHV LQ FDQFHU FHOOV

DQG PRUHRYHU D FUXFLDO DQWLYLUDO DFWLRQ ,Q SDUWLFXODU WKH GHULYDWLYHV RI LQGROH

FDUER[\OLF DFLG DQG LQGROH

FDUER[\OLF DFLG DUH ZLGHO\ XVHG LQ WKH WUHDWPHQW RI YDULRXV

GLVHDVHV KDYLQJ WKHVH FRPSRXQGV DQWLFDQFHU DQWLIXQJDO DQG LQVHFWLFLGH SURSHUWLHV

DPRQJ RWKHUV

6

$PLQR

+ LQGRO

DQWLDUUK\WKPLF

\O SURSDQRLF DFLG

NQRZQ DV

WU\SWRSKDQ LV DQ LPSRUWDQW H[DPSOH RI D ELRORJLFDOO\ DFWLYH PROHFXOH LWV PHWDEROLVP EHLQJ DVVRFLDWHG ZLWK YDULRXV SK\VLRORJLFDO IXQFWLRQV

,Q DGGLWLRQ WR SURYLGLQJ WKH VWUXFWXUDO

EDFNERQH RI SURWHLQV WU\SWRSKDQ DQ HVVHQWLDO DPLQR DFLG IXQFWLRQV DV D SUHFXUVRU IRU VHURWRQLQ DQ LPSRUWDQW QHXURWUDQVPLWWHU ZLGHO\ XVHG LQ SV\FKLDWU\ DQG QHXURORJ\

$OO

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

,Q WKLV ZRUN WKH VWDQGDUG SR

. RI LQGROH

FDUER[\OLF DFLG DQG

03D PRODU HQWKDOSLHV RI

PHWK\OLQGROH

FDUER[\OLF DFLG

LQ WKH FU\VWDOOLQH SKDVH ZHUH GHULYHG IURP WKH VWDQGDUG PRODU HQHUJLHV RI FRPEXVWLRQ PHDVXUHG E\ VWDWLF ERPE FRPEXVWLRQ FDORULPHWU\ 7KH ORZ YRODWLOLW\ RI LQGROH

FDUER[\OLF

DFLG SUHYHQWHG WKH GHWHUPLQDWLRQ RI LWV HQWKDOS\ RI VXEOLPDWLRQ E\ WKH .QXGVHQ HIIXVLRQ WHFKQLTXH VR WKH &DOYHW PLFURFDORULPHWU\ ZDV XVHG WR PHDVXUH WKH VWDQGDUG PRODU HQWKDOS\ RI VXEOLPDWLRQ RI WKLV FRPSRXQG 7KH .QXGVHQ PDVV ORVV HIIXVLRQ WHFKQLTXH ZDV XVHG WR PHDVXUH WKH YDSRU SUHVVXUH DV D IXQFWLRQ RI WHPSHUDWXUH IRU

PHWK\OLQGROH

FDUER[\OLF DFLG

7KH &ODXVLXV &ODSH\URQ HTXDWLRQ ZDV DSSOLHG WR WKH H[SHULPHQWDO YDSRU SUHVVXUH YDOXHV GHWHUPLQHG DW GLIIHUHQW WHPSHUDWXUHV IRU GHULYLQJ WKH VWDQGDUG PRODU HQWKDOS\ RI VXEOLPDWLRQ 6WDQGDUG PRODU HQWKDOS\ HQWURS\ DQG *LEEV IXQFWLRQ RI VXEOLPDWLRQ DW WKH WHPSHUDWXUH RI . ZHUH FDOFXODWHG IRU

PHWK\OLQGROH

FDUER[\OLF DFLG

&RPSXWDWLRQDO VWXGLHV ZHUH FDUULHG RXW WR FRPSOHPHQW WKH H[SHULPHQWDO ZRUN 7KH HQWKDOSLHV RI IRUPDWLRQ LQ WKH JDVHRXV SKDVH RI LQGROH

FDUER[\OLF DFLG DQG

PHWK\OLQGROH

ï ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 27

FDUER[\OLF DFLG ZHUH HVWLPDWHG E\ FRPELQLQJ WKH HQWKDOSLHV RI UHOHYDQW ZRUNLQJ UHDFWLRQV DW . FRPSXWHG DW WKH * 03

7

OHYHO RI WKHRU\ ZLWK WKH H[SHULPHQWDO HQWKDOSLHV RI

IRUPDWLRQ RI WKH DX[LOLDU\ PROHFXOHV XVHG 7KH IDFW WKDW WKH H[SHULPHQWDO YDOXHV DJUHH ZLWK WKRVH REWDLQHG XVLQJ FRPSXWDWLRQDO PHWKRGV JDYH XV FRQILGHQFH WR H[WHQG WKH FDOFXODWLRQV WR WKH VWXG\ RI LQGROH

FDUER[\OLF DFLG

PHWK\OLQGROH

FDUER[\OLF DFLG ZDV REWDLQHG FRPPHUFLDOO\ IURP 7&, DQG

PHWK\OLQGROH

FDUER[\OLF DFLG DQG

FDUER[\OLF DFLG PHWK\LQGROH

PHWK\OLQGROH

FDUER[\OLF DFLG

([SHULPHQWDO DQG &RPSXWDWLRQDO 0HWKRGV &RPSRXQG DQG SXULW\ FRQWURO ,QGROH

Š

FDUER[\OLF DFLG ZDV REWDLQHG IURP 6LJPD $OGULFK

ZLWK FHUWLILHG PROH IUDFWLRQ SXULW\ RI

UHVSHFWLYHO\ 7KH FRPSRXQGV ZHUH SXULILHG DW OHDVW WZLFH E\ VXEOLPDWLRQ

DQG

XQGHU UHGXFHG SUHVVXUH DQG WKHLU SXULW\ ZDV YHULILHG E\ JDV OLTXLG FKURPDWRJUDSK\ SHUIRUPHG RQ DQ $JLOHQW OLQNHG

' JDV FKURPDWRJUDSK HTXLSSHG ZLWK DQ +3

GLSKHQ\O DQG

WKLFNQHVV

GLPHWK\OSRO\VLOR[DQH

[

DQG ZLWK QLWURJHQ DV WKH FDUULHU JDV t

FROXPQ FURVV

PP L G [

PDVV IUDFWLRQ

P ILOP

7KH FRPEXVWLRQ

SURGXFWV ZHUH H[DPLQHG IRU FDUERQ GLR[LGH DQG WKH DYHUDJH UDWLRV RI WKH PDVV RI FDUERQ GLR[LGH UHFRYHUHG WR WKDW FDOFXODWHG IURP WKH PDVV RI VDPSOH ZHUH



DQG

PHWK\OLQGROH

FDUER[\OLF

'HWDLOV RI WKH RULJLQ DQG SXULILFDWLRQ RI WKH VDPSOHV DUH SUHVHQWHG LQ 7DEOH 6

VXSSRUWLQJ



UHVSHFWLYHO\ IRU LQGROH

FDUER[\OLF DFLG DQG

DFLG ZKHUH WKH XQFHUWDLQWLHV DUH WKH VWDQGDUG GHYLDWLRQ RI WKH PHDQ

LQIRUPDWLRQ

&RPEXVWLRQ FDORULPHWU\ 7KH FRPEXVWLRQ H[SHULPHQWV ZHUH SHUIRUPHG XVLQJ D WZLQ YDOYH ERPE ZLWK DQ LQWHUQDO YROXPH RI

GP

LQ D YHVVHO FRQWDLQHG LQ DQ LVRSHULERO FDORULPHWULF V\VWHP 7KH

DSSDUDWXV DQG WKH GHWDLOHG SURFHGXUH KDYH EHHQ SUHYLRXVO\ GHVFULEHG &RPEXVWLRQ H[SHULPHQWV ZLWK 7KHUPRFKHPLFDO 6WDQGDUG EHQ]RLF DFLG 1%6 5HIHUHQFH 0DWHULDO

M 'FX

±



-



ZHUH SHUIRUPHG WR FDOLEUDWH WKH ERPE XQGHU

FHUWLILFDWH FRQGLWLRQV &DOLEUDWLRQ H[SHULPHQWV PDGH LQ R[\JHQ DW

03D

FP RI

GHLRQL]HG ZDWHU DGGHG WR WKH ERPE 7KH HQHUJ\ HTXLYDOHQW RI WKH FDORULPHWHU HFDO ZDV GHWHUPLQHG IURP VL[ H[SHULPHQWV HFDO DGGHG WR WKH FDORULPHWHU ZDV



-

.

WKH DYHUDJH PDVV RI ZDWHU

J ð

ACS Paragon Plus Environment

Page 5 of 27

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

7KH FU\VWDOOLQH VDPSOHV ZHUH LJQLWHG LQ WKH SHOOHW IRUP DW 7 DW S

03D LQ WKH SUHVHQFH RI



. LQ R[\JHQ

FP RI ZDWHU 7KH HOHFWULFDO HQHUJ\ IRU LJQLWLRQ ZDV

GHWHUPLQHG IURP WKH FKDQJH LQ SRWHQWLDO GLIIHUHQFH DFURVV D

—) FRQGHQVHU ZKHQ

GLVFKDUJHG WKURXJK WKH SODWLQXP LJQLWLRQ ZLUH )RU WKH FRWWRQ WKUHDG IXVH &+ - Jí

,W ZDV QHFHVVDU\ WR XVH Q KH[DGHFDQH $OGULFK PDVV IUDFWLRQ !

DX[LOLDU\ FRPEXVWLRQ IRU LQGROH

DV

FDUER[\OLF DFLG FRPEXVWLRQ H[SHULPHQWV ,WV VWDQGDUG

PDVVLF HQHUJ\ RI FRPEXVWLRQ ZDV GHWHUPLQHG LQ RXU ODERUDWRU\ DV 'F X J

íûFX>

2

R



-

EHLQJ WKH XQFHUWDLQW\ TXRWHG WKH VWDQGDUG GHYLDWLRQ RI WKH PHDQ ±

7KH FDORULPHWHU WHPSHUDWXUHV ZHUH PHDVXUHG WR “ WKHUPLVWRU SUREH

7KHUPRPHWULFV

QDQRYROW PLFURRKP PHWHU $JLOHQW

. ZLWK D 6

6WDQGDUG 6HULDO 1R

IRXU ZLUH FDOLEUDWHG DQG UHFRUGHG E\ D

$ LQWHUIDFHG WR D FRPSXWHU 'DWD DFTXLVLWLRQ DQG

FRQWURO RI WKH FDORULPHWHU ZHUH SHUIRUPHG XVLQJ WKH SURJUDP /$%7(502 7KH FRUUHFWLRQV IRU QLWULF DFLG IRUPDWLRQ ZHUH EDVHG RQ HQHUJ\ RI IRUPDWLRQ RI

PRO GP

PRO

IRU WKH PRODU

+12 DT IURP 1 J 2 J DQG + 2 O $ SUHVVXUH

FRHIILFLHQW RI VSHFLILF HQHUJ\ ˜X ˜S 7 DW 7 03Dí IRU ERWK FRPSRXQGV

N-

. ZDV DVVXPHG WR EH í

-



7KH DPRXQWV RI WKH FRPSRXQGV XVHG LQ HDFK H[SHULPHQW ZHUH

EDVHG RQ WKH WRWDO PDVV RI FDUERQ GLR[LGH SURGXFHG GXULQJ WKH FRPEXVWLRQ WDNLQJ LQWR DFFRXQW WKDW IRUPHG IURP WKH FRPEXVWLRQ RI WKH FRWWRQ WKUHDG IXVH Q KH[DGHFDQH DQG WKDW ORVW GXH WR HYHQWXDO FDUERQ IRUPDWLRQ $OO WKH QHFHVVDU\ ZHLJKWLQJV ZHUH PDGH LQ D 0HWWOHU $( EDODQFH DQG VDPSOH PDVVHV ZHUH UHGXFHG WR YDFXXP )RU HDFK FRPSRXQG íûFX> ZDV FDOFXODWHG XVLQJ WKH SURFHGXUH JLYHQ E\ +XEEDUG HW DO GHQVLWLHV XVHG ZHUH ! PHWK\OLQGROH

J FP

IRU LQGROH

7KH OLWHUDWXUH YDOXHV RI WKH VSHFLILF

FDUER[\OLF DFLG DQG !

J FP

IRU

FDUER[\OLF DFLG

7KH UHODWLYH DWRPLF PDVVHV XVHG IRU WKH HOHPHQWV ZHUH WKRVH UHFRPPHQGHG E\ WKH ,83$& &RPPLVVLRQ LQ

+LJK WHPSHUDWXUH &DOYHW PLFURFDORULPHWU\ $ KLJK WHPSHUDWXUH &DOYHW PLFURFDORULPHWHU 6HWDUDP PRGHO +7 WKH VWDQGDUG PRODU HQWKDOS\ RI VXEOLPDWLRQ RI LQGROH

ZDV XVHG WR PHDVXUH

FDUER[\OLF DFLG 7KH GHVFULSWLRQ RI WKH

DSSDUDWXV DQG H[SHULPHQWDO WHFKQLTXH KDYH EHHQ GHVFULEHG HOVHZKHUH 7KLQ JODVV FDSLOODU\ WXEHV VHDOHG DW RQH HQG RQH FRQWDLQLQJ WKH FU\VWDOOLQH VDPSOH DERXW ± PJ DQG WKH RWKHU EHLQJ WKH UHIHUHQFH WXEH ZHUH VLPXOWDQHRXVO\ GURSSHG LQWR WKH KRW ñ ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

UHDFWLRQ YHVVHO KHOG DW 7

Page 6 of 27

. DQG DIWHU WKHUPDO VWDELOL]DWLRQ UHPRYHG E\ YDFXXP

VXEOLPDWLRQ 1HDUO\ HTXDO JODVV FDSLOODU\ WXEHV ZLWKLQ “

J ZHUH XVHG WR PLQLPL]H WKH

WKHUPDO FRUUHFWLRQV WKDW ZHUH GHWHUPLQHG LQ VHSDUDWH H[SHULPHQWV

7KH PLFURFDORULPHWHU

ZDV FDOLEUDWHG LQ VLWX DW WKH H[SHULPHQWDO WHPSHUDWXUH 7

. E\ SHUIRUPLQJ

VXEOLPDWLRQ H[SHULPHQWV ZLWK DQWKUDFHQH LQ WKH VDPH H[SHULPHQWDO FRQGLWLRQV XVLQJ WKH UHSRUWHG VWDQGDUG PRODU HQWKDOS\ RI VXEOLPDWLRQ FRQVWDQW GHWHUPLQHG IRU LQGROH .





N- PROí

7KH FDOLEUDWLRQ

FDUER[\OLF DFLG VXEOLPDWLRQ VWXG\ ZDV NFDO

REWDLQHG DV WKH DYHUDJH RI VL[ LQGHSHQGHQW H[SHULPHQWV ZLWK WKH

TXRWHG XQFHUWDLQW\ EHLQJ WKH VWDQGDUG GHYLDWLRQ RI WKH PHDQ

9DSRU SUHVVXUHV PHDVXUHPHQWV 7KH YDSRU SUHVVXUHV LQ WKH UDQJH RI

WR

3D RI

PHWK\OLQGROH

FDUER[\OLF DFLG ZHUH

PHDVXUHG DW VHYHUDO WHPSHUDWXUHV E\ .QXGVHQ HIIXVLRQ WHFKQLTXH XVLQJ DQ DSSDUDWXV WKDW ZDV EXLOW LQ RXU ODERUDWRU\ DQG KDV DOUHDG\ EHHQ GHVFULEHG SUHYLRXVO\

7KLV DSSDUDWXV DOORZV

WKH VLPXOWDQHRXV RSHUDWLRQ RI QLQH DOXPLQLXP HIIXVLRQ FHOOV DQG KDV EHHQ WHVWHG E\ PHDVXULQJ WKH YDSRU SUHVVXUHV EHWZHHQ

3D DQG

3D RI VHYHUDO UHIHUHQFH FRPSRXQGV EHQ]RLF DFLG

SKHQDQWKUHQH DQWKUDFHQH EHQ]DQWKURQH DQG 7KH YDSRU SUHVVXUHV ZHUH PHDVXUHG LQ WKH UDQJH

WULSKHQ\OEHQ]HQH WR

3D RYHU WHPSHUDWXUH UDQJHV RI FD

. 7KH PDVV VXEOLPHG ûP RI WKH VDPSOHV GXULQJ D FRQYHQLHQW HIIXVLRQ WLPH SHULRG W LV GHWHUPLQHG E\ ZHLJKLQJ WKH HIIXVLRQ FHOOV WR “

PJ EHIRUH DQG DIWHU WKH HIIXVLRQ SHULRG

7KH YDSRU SUHVVXUH S DW WKH WHPSHUDWXUH 7 LV FDOFXODWHG E\ WKH HTXDWLRQ

S

'P $RZR W

S57 0

ZKHUH 0 LV WKH PRODU PDVV RI WKH HIIXVLQJ YDSRU 5 LV WKH JDV FRQVWDQW $R LV WKH DUHD RI WKH HIIXVLRQ KROH DQG ZR LV WKH &ODXVLQJ SUREDELOLW\ IDFWRU 7KH YDOXHV RI $R DQG ZR RI WKH HIIXVLRQ RULILFHV PDGH LQ SODWLQXP IRLO RI

PP WKLFNQHVV DUH UHJLVWHUHG LQ 7DEOH 6 RI

WKH VXSSRUWLQJ LQIRUPDWLRQ

&RPSXWDWLRQDO GHWDLOV ,Q WKH SUHVHQW ZRUN WKH DEVROXWH HQWKDOSLHV DW 7 PHWK\OLQGROH PHWK\OLQGROH

FDUER[\OLF DFLG

PHWK\OLQGROH

FDUER[\OLF DFLG DQG

. RI LQGROH

FDUER[\OLF DFLG

FDUER[\OLF DFLG LQGROH

PHWK\LQGROH

FDUER[\OLF DFLG

FDUER[\OLF DFLG DQG DOO WKH DX[LOLDU\

VSHFLHV FRQVLGHUHG ZHUH FDOFXODWHG XVLQJ WKH FRPSRVLWH * 03

DSSURDFK

7KLV SURWRFRO ò

ACS Paragon Plus Environment

Page 7 of 27

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

LQYROYHV DQ LQLWLDO JHRPHWU\ RSWLPL]DWLRQ DW WKH +DUWUHH )RFN +) OHYHO ZLWK WKH ± EDVLV

*G

DQG WKH VXEVHTXHQW GHWHUPLQDWLRQ RI WKH KDUPRQLF IUHTXHQFLHV ZKLFK DUH WKHQ VFDOHG

E\ D IDFWRU RI

WR WDNH DFFRXQW RI NQRZQ GHILFLHQFLHV DW WKLV OHYHO

IUHTXHQFLHV DUH XVHG WR HYDOXDWH WKH ]HUR SRLQW HQHUJ\ ( =3( HTXLOLEULXP JHRPHWU\ LV IXUWKHU UHILQHG DW WKH 03 )XOO

±

7KHVH

DQG WKHUPDO HIIHFWV 7KH

* G OHYHO XVLQJ DOO HOHFWURQV

IRU WKH FDOFXODWLRQ RI FRUUHODWLRQ HQHUJ\ )LQDOO\ D VHULHV RI VLQJOH SRLQW HQHUJ\ FDOFXODWLRQV LQFOXGLQJ 4&,6' 7

TXDGUDWLF FRQILJXUDWLRQ LQWHUDFWLRQ LQFOXGLQJ VLQJOH DQG GRXEOH

H[FLWDWLRQV ZLWK WULSOH H[FLWDWLRQV EHLQJ WDNHQ LQWR DFFRXQW SHUWXUEDWLYHO\ XVLQJ WKH

*G

EDVLV VHW LV WKHQ SHUIRUPHG DQG WKH UHVXOWV SURSHUO\ FRUUHFWHG DQG FRPELQHG LQWR D ILQDO HQHUJ\ ZKLFK LV HIIHFWLYHO\ DW WKH 4&,6' 7 )&

* GI S OHYHO

R 7KH YDOXHV RI WKH PRODU KHDW FDSDFLW\ LQ WKH JDVHRXV SKDVH DW GLIIHUHQW WHPSHUDWXUHV &S P J

KDYH EHHQ GHULYHG IURP VWDWLVWLFDO WKHUPRG\QDPLFV FDOFXODWHG DW WKH 5+) *DXVVLDQ

XVLQJ WKH YLEUDWLRQDO IUHTXHQFLHV

* G OHYHO RI WKHRU\ $OO FDOFXODWLRQV ZHUH SHUIRUPHG XVLQJ WKH

VHULHV RI SURJUDPV

WKH DWRPV LQ PROHFXOHV $,0

ZDYHIXQFWLRQ KDYH EHHQ FDUULHG RXW E\ XVLQJ WKH $,0$// RUELWDO 1%2 DQDO\VHV E\ XVLQJ WKH 1%2

PRGXOH

DQDO\VHV RI WKH

SURJUDP DQG WKH QDWXUDO ERQG

FRXSOHG WR WKH *DXVVLDQ

FRGH

5HVXOWV &RPEXVWLRQ FDORULPHWU\ 'HWDLOHG UHVXOWV RI DOO FRPEXVWLRQ H[SHULPHQWV SHUIRUPHG IRU LQGROH PHWK\OLQGROH

FDUER[\OLF DFLG DQG

FDUER[\OLF DFLG DUH JLYHQ LQ 7DEOHV 6 6 UHVSHFWLYHO\

7KH PHDQ YDOXH RI WKH VWDQGDUG PDVVLF HQHUJLHV RI FRPEXVWLRQ æûFXƒç IRU DOO FRPEXVWLRQ H[SHULPHQWV RI HDFK FRPSRXQG DQG WKH VWDQGDUG GHYLDWLRQ RI WKH PHDQ YDOXH WKH GHULYHG YDOXHV RI WKH VWDQGDUG PRODU HQHUJLHV ¨F 8RP FU DQG HQWKDOSLHV ¨F +RP FU IRU WKH FRPEXVWLRQ UHDFWLRQV GHVFULEHG E\ FKHPLFDO HTXDWLRQV

DQG

UHVSHFWLYHO\ DV ZHOO DV WKH VWDQGDUG

PRODU HQWKDOS\ RI IRUPDWLRQ ¨I +RP FU IRU HDFK RI WKH WZR FRPSRXQGV VWXGLHG DW 7 . DUH JLYHQ LQ 7DEOH & + 12 :FU;

2 :J;: &2 :J;

& + 12 :FU;

2 :J;: &2 :J;

+ 2:O; + 2:O;

1 :J; 1 :J;

ó ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 27

7$%/( 03D PDVVLF HQHUJLHV RI FRPEXVWLRQ èF XR Ä PRODU HQHUJLHV RI FRPEXVWLRQ

'HULYHG VWDQGDUG SR

¨F 8RP VWDQGDUG PRODU HQWKDOSLHV RI FRPEXVWLRQ ¨F +RP DQG VWDQGDUG PRODU HQWKDOSLHV RI IRUPDWLRQ ¨ˆ +RP IRU WKH FU\VWDOOLQH FRPSRXQGV DW 7

.

ÅèF XR Ä -ÂJ

&RPSRXQG ,QGROH

FDUER[\OLF DFLG

0HWK\OLQGROH

FDUER[\OLF DFLG

D

ŨF 8RP

E

ŨF +RP N-  PRO

N- Â PRO

E

ŨI +RP

E

N- Â PRO

















D

0HDQ YDOXH DQG VWDQGDUG GHYLDWLRQ RI WKH PHDQ 7KH XQFHUWDLQWLHV DUH WZLFH WKH RYHUDOO VWDQGDUG GHYLDWLRQ RI WKH PHDQ DQG LQFOXGH WKH FRQWULEXWLRQV IURP WKH FDOLEUDWLRQ ZLWK EHQ]RLF DFLG DQG IURP WKH HQHUJ\ RI FRPEXVWLRQ RI DX[LOLDU\ PDWHULDOV

E

7KH XQFHUWDLQWLHV DVVLJQHG WR WKH VWDQGDUG PRODU HQHUJLHV RI FRPEXVWLRQ DQG VWDQGDUG PRODU HQWKDOSLHV RI FRPEXVWLRQ DUH LQ HDFK FDVH WZLFH WKH RYHUDOO VWDQGDUG GHYLDWLRQ RI WKH PHDQ DQG LQFOXGH WKH XQFHUWDLQWLHV LQ FDOLEUDWLRQ DQG LQ WKH YDOXHV RI DX[LOLDU\ TXDQWLWLHV XVHG 7R REWDLQ ¨I +RP FU IURP ¨… +RP FU WKH VWDQGDUG PRODU HQWKDOSLHV RI IRUPDWLRQ RI &2 J DQG + 2 O DW 7

. ±



N- PRO

DQG ±



N- PRO

UHVSHFWLYHO\ ZHUH XVHG

+LJK WHPSHUDWXUH &DOYHW PLFURFDORULPHWU\ 0HDVXUHPHQWV RI WKH VWDQGDUG PRODU HQWKDOS\ RI VXEOLPDWLRQ RI LQGROH

FDUER[\OLF DFLG E\

&DOYHW PLFURFDORULPHWU\ DV ZHOO DV WKH DVVRFLDWHG XQFHUWDLQW\ JLYHQ E\ LWV VWDQGDUG GHYLDWLRQ RI WKH PHDQ DUH JLYHQ LQ 7DEOH RI VXEOLPDWLRQ DW 7

7KH XQFHUWDLQW\ DVVRFLDWHG WR WKH VWDQGDUG PRODU HQWKDOS\

. LV WZLFH WKH VWDQGDUG GHYLDWLRQ RI WKH PHDQ DQG LQFOXGH WKH

XQFHUWDLQWLHV DVVRFLDWHG ZLWK WKH FDOLEUDWLRQ SURFHVV 7KH REVHUYHG HQWKDOSLHV RI SKDVH WUDQVLWLRQ ZHUH FRUUHFWHG WR 7

¨JFU +RP :

. XVLQJ WKH HTXDWLRQ

J7

.; ¨FU O

R . +P

Åì

7

&SR P :J; G7

ZKHUH 7 LV WKH WHPSHUDWXUH RI WKH KRW UHDFWLRQ FHOOV DQG &RS P :J; LV WKH JDV SKDVH PRODU KHDW FDSDFLW\ GHULYHG IURP VWDWLVWLFDO WKHUPRG\QDPLFV XVLQJ WKH YLEUDWLRQDO IUHTXHQFLHV REWDLQHG DW WKH +) LQGROH

* G OHYHO VFDOHG E\ D IDFWRU RI

U

7KH &RS P :J; I:7; REWDLQHG IRU

FDUER[\OLF DFLG LV UHSUHVHQWHG E\

ô ACS Paragon Plus Environment

Page 9 of 27

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

&SR P - Â PRO Â .

Å

:7 .; Å

î

î

:7 .;

î

:7 .; Å

7KH JDV SKDVH PRODU KHDW FDSDFLW\ YDOXHV DV D IXQFWLRQ RI WKH WHPSHUDWXUH EHWZHHQ

DQG

. DUH JLYHQ LQ 6XSSRUWLQJ ,QIRUPDWLRQ 7DEOH 6 7$%/( 6WDQGDUG SR

03D PRODU HQWKDOS\ RI VXEOLPDWLRQ IRU LQGROH 1XPEHU RI

&RPSRXQG ,QGROH

H[SHULPHQWV

7_ .

FDUER[\OLF DFLG DW 7 R` . +P

J7

¨FU

R . +P :J;

N- Â PRO

N- Â PRO

FDUER[\OLF DFLG

¨7



. a

¨JFU +RP :

.;

N- Â PRO “

D

X7 “ . 0HDQ YDOXH DQG VWDQGDUG GHYLDWLRQ RI WKH PHDQ F 7KH XQFHUWDLQW\ LV WZLFH WKH RYHUDOO VWDQGDUG GHYLDWLRQ RI WKH PHDQ DQG LQFOXGH WKH FRQWULEXWLRQV IURP WKH FDOLEUDWLRQ

E

9DSRU SUHVVXUHV PHDVXUHPHQWV 7KH H[SHULPHQWDO HIIXVLRQ UHVXOWV REWDLQHG IRU LQ 7DEOH 6

7KH SORW RI OQ S DJDLQVW

FDUER[\OLF DFLG LV VKRZQ LQ )LJXUH

PHWK\OLQGROH

FDUER[\OLF DFLG DUH FRPSLOHG

7 IRU WKH UHVXOWV REWDLQHG IRU WKH

PHWK\OLQGROH

%HWZHHQ VPDOO LQWHUYDOV RI WHPSHUDWXUH WKLV

UHSUHVHQWDWLRQ FDQ EH FRQVLGHUHG DV D VWUDLJKW OLQH ZKHUH LWV VORSH DOORZV WKH FDOFXODWLRQ RI WKH HQWKDOS\ RI VXEOLPDWLRQ RI WKH FRPSRXQG DW WKH PHDQ WHPSHUDWXUH RI WKH H[SHULPHQWDO UDQJH XVLQJ WKH LQWHJUDWHG IRUP RI WKH &ODXVLXV &ODSH\URQ HTXDWLRQ OQ:S 3D; D Å E:7 .; LQWHJUDWHG IRUP RI WKH &ODXVLXV &ODSH\URQ HTXDWLRQ OQ:S 3D; D Å E:7 .; J

FRQVWDQW DQG E ¨FU O +P:Ã7Ä; 5 DUH SUHVHQWHG LQ 7DEOH

7KH

ZKHUH = LV D

WRJHWKHU ZLWK WKH FDOFXODWHG VWDQGDUG

GHYLDWLRQV DQG WKH VWDQGDUG PRODU HQWKDOS\ RI VXEOLPDWLRQ DW WKH PHDQ WHPSHUDWXUH Ã7Ä IRU HDFK HIIXVLRQ RULILFH XVHG DQG IRU WKH JOREDO WUHDWPHQW RI DOO WKH :S 7; SRLQWV

õ ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ACS Paragon Plus Environment

Page 10 of 27

Page 11 of 27

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

R

ZKHUH ¨JFU &S P : E\ 0RQWH HW DO

.;

- Â . Â PRO

Å

7KLV HTXDWLRQ LV D UHDUUDQJHPHQW RI HTXDWLRQ

R

¨JFU &S P :

.;

R

¨JFU &S P:

.;

- Â . Â PRO

DW 7

.; _ .; _

&SR P :J

Å[

*G

SURSRVHG

SURSRVHG E\ &KLFNRV HW DO

&SR P :FU

Å[

9LEUDWLRQDO IUHTXHQFLHV IURP +) ± &SR P :J;

ZDV FDOFXODWHG XVLQJ HTXDWLRQ

FDOFXODWLRQV ZHUH XVHG WR FDOFXODWH RI

. DV GHVFULEHG LQ WKH FRPSXWDWLRQDO GHWDLOV

VHFWLRQX

)RU WKLV FRPSRXQG WKH YDOXHV DW 7

. RI WKH VWDQGDUG PRODU HQWKDOS\ RI

VXEOLPDWLRQ WKH VWDQGDUG PRODU HQWURS\ RI VXEOLPDWLRQ FDOFXODWHG E\ WKH HTXDWLRQ Lm L

ZHUH

3D DQG WKH VWDQGDUG PRODU *LEEV HQHUJ\ RI VXEOLPDWLRQ DUH UHSRUWHG LQ 7DEOH

¨JFU 6RP:

.;

¨JFU 6PkÃ7Ä S:Ã7Ä;o

¨JFU &S P OQ l R

SR p t5 OQ l p Ã7Ä S:Ã7Ä;

7$%/( 03D PRODU HQWKDOS\ ¨JFU +RP HQWURS\ ¨JFU 6RP DQG *LEEV HQHUJ\ . IRU PHWK\OLQGROH FDUER[\OLF DFLG D

9DOXHV RI WKH VWDQGDUG SR ¨JFU *RP RI VXEOLPDWLRQ DW 7

N- Â PRO 0HWK\OLQGROH D

¨JFU 6RP

¨JFU +RP

&RPSRXQG FDUER[\OLF DFLG

¨JFU *RP

- Â . Â PRO



N- Â PRO





8QFHUWDLQWLHV FDOFXODWHG WKURXJK WKH 566 5RRW 6XP 6TXDUH PHWKRG

7KH VWDQGDUG PRODU HQWKDOSLHV RI IRUPDWLRQ LQ WKH JDVHRXV VWDWH DW 7 REWDLQHG IRU WKH LQGROH

FDUER[\OLF DFLG DQG

PHWK\OLQGROH

. ZHUH

FDUER[\OLF DFLG E\ WKH

DGGLWLRQ RI WKH GHULYHG VWDQGDUG PRODU HQWKDOSLHV RI IRUPDWLRQ LQ WKH FU\VWDOOLQH VWDWH DQG WKH VWDQGDUG PRODU HQWKDOSLHV RI VXEOLPDWLRQ 7KH UHVXOWV DUH VXPPDUL]HG LQ 7DEOH

$OWKRXJK

WKH YDSRU SUHVVXUH PHDVXUHPHQW PHWKRG VHHP WR JLYH EHWWHU UHVXOWV WKDQ WKH FDORULPHWULF WHFKQLTXHV

VHYHUDO VWXGLHV ZKHUH ERWK PHWKRGV ZHUH XVHG LQ WKH GHWHUPLQDWLRQ RI

íí ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 27

HQWKDOSLHV RI VXEOLPDWLRQ GHPRQVWUDWH WKDW WKH UHVXOWV REWDLQHG E\ WKH WZR GLIIHUHQW WHFKQLTXHV DUH FRPSDUDEOH 7$%/( 6WDQGDUG SR PHWK\OLQGROH

03D PRODU HQWKDOSLHV RI IRUPDWLRQ IRU LQGROH

FDUER[\OLF DFLG LQ ERWK FU\VWDOOLQH DQG JDVHRXV SKDVHV DQG VWDQGDUG PRODU HQWKDOSLHV

RI VXEOLPDWLRQ DW 7

.D ¨I +RP :FU;

&RPSRXQG

N- Â PRO ,QGROH

FDUER[\OLF DFLG

0HWK\OLQGROH D

FDUER[\OLF DFLG DQG

FDUER[\OLF DFLG

¨I +RP :J;

¨JFU +RP

N- Â PRO

N- Â PRO













8QFHUWDLQWLHV FDOFXODWHG WKURXJK WKH 566 5RRW 6XP 6TXDUH PHWKRG

&RPSXWDWLRQDO FDOFXODWLRQV %RWK WKH LQGROH ULQJ DQG WKH FDUER[\O JURXS SRVVHVV GHORFDOL]HG HOHFWURQV LQ Œ V\PPHWU\ RUELWDOV DQG H[WHQGHG HOHFWURQ FRQMXJDWLRQ SKHQRPHQD LQYROYLQJ ERWK IUDJPHQWV LV H[SHFWHG WR RFFXU LI WKH\ DGRSW PXWXDO FRSODQDU RU TXiVL FRSODQDU RULHQWDWLRQV 7KXV SODQDU FRQIRUPDWLRQ RI WKHVH PROHFXOHV LV OLNHO\ WR EH HQHUJHWLFDOO\ IDYRUHG D FRQMHFWXUH ZKLFK KDV LQGHHG EHHQ FRQILUPHG IRU DOO WKH VWXGLHG LQGROH FDUER[\OLF DFLGV GHULYDWLYHV VLQFH WKH\ DUH REVHUYHG WR KDYH D SODQDU VWUXFWXUH DW WKHLU RSWLPL]HG 03 )XOO

±

* G JHRPHWULHV VHH

)LJXUH

íî ACS Paragon Plus Environment

Page 13 of 27

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

The Journal of Physical Chemistry

,QGROH

)LJXUH

,QGROH

0HWK\OLQGROH

FDUER[\OLF DFLG

0HWK\OLQGROH

FDUER[\OLF DFLG

03 )XOO

PHWK\OLQGROH PHWK\OLQGROH

,QGROH

FDUER[\OLF DFLG

FDUER[\OLF DFLG

0HWK\OLQGROH

0HWK\OLQGROH

FDUER[\OLF DFLG

FDUER[\OLF DFLG

* G RSWLPL]HG PRVW VWDEOH FRQILJXUDWLRQV IRU WKH LQGROH

FDUER[\OLF DFLG

PHWK\OLQGROH

FDUER[\OLF DFLG DQG

PHWK\LQGROH

FDUER[\OLF DFLG LQGROH

FDUER[\OLF DFLG

FDUER[\OLF DFLG

FDUER[\OLF DFLG

FDUER[\OLF DFLG LV VOLJKWO\ PRUH VWDEOH WKDQ LQGROH

FDUER[\OLF DFLG EHFDXVH RI D

VWDELOL]LQJ + ERQG W\SH LQWHUDFWLRQ ZKLFK RFFXUV IRU WKH ILUVW V\VWHP DQG LQYROYHV WKH & 2 R[\JHQ DWRP DV WKH K\GURJHQ DWRP DFFHSWRU DQG WKH &±+ QHDUE\ ERQG RI WKH EHQ]HQLF ULQJ DV WKH K\GURJHQ GRQRU ZKLFK LV QRW OLNHO\ WR RFFXU LQ WKH RWKHU LVRPHU VLQFH LW ZRXOG LQYROYH D YHU\ EHQW

ž ±

ž DQG WKXV H[WUHPHO\ ZHDN 1±+«2 RU &±+«2 LQWHUDFWLRQ 7KLV

FRQVWUDLQW LV D GLUHFW FRQVHTXHQFH RI WKH GRQRU DQG DFFHSWRU IUDJPHQWV EHLQJ GLUHFWO\ ERQGHG WR WKH VDPH S\UUROH ULQJ LQ WKLV LVRPHU $ VLPLODU + ERQG W\SH LQWHUDFWLRQ LV KRZHYHU REVHUYHG IRU

PHWK\OLQGROH

PHWK\OLQGROH

FDUER[\OLF DFLG ZKLOH

PHWK\OLQGROH

FDUER[\OLF DFLG DQG

FDUER[\OLF DFLG DUH RQ WKHLU KDQG VWDELOL]HG E\ + ERQG W\SH LQWHUDFWLRQV íï ACS Paragon Plus Environment

The Journal of Physical Chemistry

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 27

LQYROYLQJ WKH LQ SODQH &±+ ERQG RI WKH PHWK\O VXEVWLWXHQW DQG RQH RI WKH R[\JHQ DWRPV RI WKH FDUER[\O VXEVWLWXHQW 1RWH WKDW WKH ODVW VLWXDWLRQV LQYROYH GRQRU DQG DFFHSWRU IUDJPHQWV QRW GLUHFWO\ ERQGHG WR WKH S\UUROH ULQJ WKLV IDFW DOORZLQJ WKH IRUPDWLRQ RI PXFK PRUH OLQHDUL]HG + ERQG W\SH LQWHUDFWLRQV )LQDOO\ IRU

PHWK\OLQGROH

FDUER[\OLF DFLG ERWK W\SHV RI + ERQG

W\SH LQWHUDFWLRQV DUH DOORZHG WR RFFXU WKLV LVRPHU LV FRQVHTXHQWO\ WKH PRVW VWDEOH RI WKH GLVVXEVWLWXWHG LVRPHUV :H UHIHU DOVR WKDW HDFK RI WKH DERYH PHQWLRQHG LQWHUDFWLRQV KDV EHHQ FKDUDFWHUL]HG DV D WUXH FKHPLFDO ERQG WKURXJK DQDO\VHV RI WKH UHOHYDQW % /