Ultrafast Broad-Band Optical Limiting in Simple Hydrazone Derivatives

Jun 26, 2018 - College of Chemistry, Chemical Engineering and Materials Science of .... state S0, excited state S1, and higher excited state S2 on the...
0 downloads 0 Views 2MB Size
Subscriber access provided by TUFTS UNIV

C: Plasmonics; Optical, Magnetic, and Hybrid Materials

Ultrafast Broadband Optical Limiting in Simple Hydrazone Derivatives with #-Conjugated System: The Effect of Two-Photon Induced Singlet State Absorption Jidong Jia, Xingzhi Wu, Yu Fang, Junyi Yang, Xiao Guo, Qianyan Xu, Yanbing Han, and Yinglin Song J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.8b02149 • Publication Date (Web): 26 Jun 2018 Downloaded from http://pubs.acs.org on June 29, 2018

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 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 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.

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 34 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

8OWUDIDVW %URDGEDQG 2SWLFDO /LPLWLQJ LQ 6LPSOH +\GUD]RQH 'HULYDWLYHV ZLWK ^ &RQMXJDWHG 6\VWHP 7KH (IIHFW RI 7ZR 3KRWRQ ,QGXFHG 6LQJOHW 6WDWH $EVRUSWLRQ Jidong Jia,‚ Xingzhi Wu,Á Yu Fang,Á Junyi Yang,‚ Xiao Guo,† Qianyan Xu,‚ Yanbing Han __ and Yinglin Song

‚ __



'HSDUWPHQW RI SK\VLFV 6RRFKRZ 8QLYHUVLW\ 6X]KRX

Á

6FKRRO RI 0DWKHPDWLFV DQG 3K\VLFV 6X]KRX 8QLYHUVLW\ RI 6FLHQFH DQG 7HFKQRORJ\ 6X]KRX



&ROOHJH RI FKHPLVWU\ &KHPLFDO (QJLQHHULQJ DQG 0DWHULDOV 6FLHQFH RI 6RRFKRZ 8QLYHUVLW\ 6X]KRX

&KLQD

&KLQD ||

'HSDUWPHQW RI SK\VLFV +DUELQ LQVWLWXWH RI WHFKQRORJ\ +DUELQ

ACS Paragon Plus Environment

&KLQD

&KLQD

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 34

$EVWUDFW

7ZR VLPSOH K\GUD]RQH GHULYDWLYHV $

$

OLQNHG ZLWK GLIIHUHQW ^ FRQMXJDWHG V\VWHP DUH GHVLJQHG DQG

V\QWKHVL]HG WR UHDFK XOWUDIDVW EURDGEDQG RSWLFDO OLPLWLQJ 2/ XQGHU GLIIHUHQW SXOVH ZLGWKV 7R H[SORLW YDULRXV YLUWXHV RI WZR SKRWRQ DEVRUSWLRQ 73$ LQGXFHG H[FLWHG VWDWH DEVRUSWLRQ 73$ (6$

(6$ LV

VXFFHVVIXOO\ HVWDEOLVKHG RQ D VLQJOHW VWDWH %RWK WKH WZR FRPSRXQGV VKRZ D EURDGEDQG (6$ UDQJHV IURP QP WR

QP DQG UHODWLYHO\ ORQJ (6$ OLIHWLPH $ GLVSOD\V D ODUJHU EURDGEDQG UHYHUVH VDWXUDEOH DEVRUSWLRQ

WKDQ $

LQ WKH PXOWL ZDYHOHQJWKV = VFDQ H[SHULPHQWV )XUWKHUPRUH VXSHULRU RSWLFDO OLPLWLQJ 2/

SHUIRUPDQFH LQ $ LV VKRZHG IURP WKUHVKROGV

î

- FP DW

QP WR QP XQGHU

QP XQGHU ERWK IHPWRVHFRQGV DQG SLFRVHFRQGV 7KH IV DUH ORZHU WKDQ PRVW RI WKH 2/ PDWHULDOV UHSRUWHG

SUHYLRXVO\ 2XU UHVXOWV LQGLFDWH WKDW WKH VLQJOHW EDVHG 73$ (6$ LV D IHDVLEOH PHWKRG WR DFKLHYH 2/ ZLWK KLJK OLQHDU WUDQVPLWWDQFH EURDGEDQG DQG XOWUDIDVW UHVSRQVH 6LPSOH PROHFXOHV ZLWK SURSHU GHVLJQ GLVSOD\ VXSHULRU 2/ SHUIRUPDQFH ZKLFK RIIHU XV D SUDFWLFDO ZD\ WR DFKLHYH XOWUDIDVW EURDGEDQG 2/ LQ ORZ FRVW RUJDQLF PDWHULDOV

ACS Paragon Plus Environment

Page 3 of 34 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

:LWK WKH GHYHORSPHQW RI ODVHU WHFKQRORJ\ SXOVHG ODVHU KDV EHHQ ZLGHO\ DSSOLHG LQ VFLHQFH DQG LQGXVWU\ DUHDV 7KH HPSOR\PHQWV RI WKHVH LQWHQVH ODVHU VRXUFHV FUHDWH KLJKHU GHPDQGV IRU WKH SURSHU SURWHFWLRQ RI GHWHFWRUV DQG KXPDQ H\HV LQ VXFK V\VWHP

2SWLFDO OLPLWLQJ 2/ DV RQH RI WKH PRVW LPSRUWDQW DSSOLFDWLRQV

RI QRQOLQHDU RSWLFV KDV EHHQ FRQVLGHUHG DQ LGHDO PHFKDQLVP IRU ODVHU SURWHFWLRQ VLQFH LW IRFXVHV RQ WKH DEVRUELQJ RI H[FHVVLYH ODVHU HQHUJ\ ZLWKRXW D FRPSURPLVH RI OLQHDU WUDQVPLWWDQFH 7KH PHFKDQLVPV DQG PDWHULDOV RI RSWLFDO OLPLWLQJ KDYH EHHQ LQYHVWLJDWHG IRU GHFDGHV \HW LW VWLOO UHPDLQV D FKDOOHQJH WR FRPELQH KLJK WUDQVPLWWDQFH VWURQJ RSWLFDO OLPLWLQJ XOWUDIDVW DQG EURDGEDQG UHVSRQVH LQ D VLQJOH RSWLFDO PDWHULDO

([FLWHG VWDWH DEVRUSWLRQ (6$ SOD\V D NH\ UROH LQ 2/ ,Q PRVW 2/ PDWHULDOV (6$ LV HVWDEOLVKHG RQ D WULSOHW VWDWH

(OHFWURQV DUH ILUVWO\ SURPRWHG WR D VLQJOHW VWDWH E\ GLUHFWO\ DEVRUELQJ LQFLGHQW SKRWRQV DQG WKHQ

SRSXODWH WKH WULSOHW VWDWH YLD LQWHUV\VWHP FURVVLQJ ,6& +RZHYHU WKLV SURFHVV LQWURGXFH WZR GLVDGYDQWDJHV ILUVW OLQHDU WUDQVPLWWDQFH LV UHODWLYHO\ ORZ EHFDXVH WKH 2/ PDWHULDOV DUH UHTXLUHG WR ZRUN LQ UHVRQDQW DEVRUSWLRQ EDQG WR DFWLYDWH (6$ 6HFRQG WKH W\SLFDO ,6& WLPHV LQ 2/ PDWHULDOV UDQJH IURP SLFRVHFRQGV WR VHYHUDO QDQRVHFRQGV

ZKLFK OLPLWV WKH UHVSRQGLQJ WLPH WRZDUGV XOWUDIDVW SXOVHV 7R RYHUFRPH WKHVH

GLVDGYDQWDJHV DQG DFKLHYH XOWUDIDVW EURDGEDQG 2/ WZR SKRWRQ DEVRUSWLRQ 73$

LQGXFHG (6$ 73$

(6$ EDVHG RQ VLQJOHW VWDWH LV HPSOR\HG ,Q WKLV 2/ PHFKDQLVP WZR SKRWRQV LQVWHDG RI RQH DUH DEVRUEHG WR LQGXFH (6$ H[WUHPHO\ KLJK WUDQVPLWWDQFH FRXOG EH DFKLHYHG LQ VXFK FDVH VLQFH 73$ RFFXUV IDU DZD\ IURP WKH UHVRQDQW ZDYHOHQJWKV

)XUWKHUPRUH VLQJOHW EDVHG (6$ RPLWV WKH ,6& SURFHVV ZKLFK DZDUGV XOWUDIDVW

UHVSRQGLQJ WR WKH 2/ PDWHULDOV ,Q RXU SUHYLRXV ZRUN DWWHQWLRQ ZDV SDLG WR WKH IOXRUHVFHQFH HPLWWLQJ RUJDQLF PROHFXOHV ZLWK Œ FRQMXJDWLRQ V\VWHP

7KH VXSSUHVVHG ,6& DQG HQKDQFHG 73$ PDGH WKHVH SRO\F\FOLF

DURPDWLF K\GURFDUERQ 3$+ FRPSRXQGV SURPLVLQJ XOWUDIDVW 2/ PDWHULDOV ZLWK EURDGEDQG UHVSRQVH ;LDR HW DO DFKLHYHG XOWUDIDVW EURDGEDQG 2/ LQ D VLPSOH S\UHQH EDVHG DV\PPHWU\ PROHFXOH ZLWK LQWUDPROHFXODU

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

FKDUJH WUDQVIHU

Page 4 of 34

:X HW DO GHVLJQHG D VHULHV RI VSLQGOH W\SH PROHFXOHV IRU VLQJOHW EDVHG 73$ (6$ DQG

UHDOL]H WKH VLPXOWDQHRXVO\ HQKDQFLQJ RI ERWK 73$

(6$ YLD H[WHQGLQJ Œ FRQMXJDWLRQ V\VWHP :LWK WKH

UHVXOWV IURP ERWK H[SHULPHQWV DQG WKHRUHWLFDO DQDO\VLV 73$ (6$ RQ VLQJOHW VWDWH ZDV SURYHQ D IHDVLEOH ZD\ WR DFKLHYH XOWUDIDVW EURDGEDQG UHYHUVH VDWXUDEOH DEVRUSWLRQ IURP YLVLEOH WR QHDU LQIUDUHG

&KHPLFDO VWUXFWXUHV RI $ DQG $

6FKHPH

%DVHG RQ WKHVH UHVXOWV ZH IXUWKHU LQYHVWLJDWHG WKH XOWUDIDVW EURDGEDQG 2/ LQ VLPSOH K\GUD]RQH GHULYDWLYHV ,Q

WKLV

ZRUN

WZR

VLPSOH

\OPHWK\OHQH K\GUD]LQ\O EHQ]R>d@WKLD]ROH

K\GUD]RQH

GHULYDWLYHV

DQG

$ $

(

S\UHQ (

GLPHWKR[\EHQ]\OLGHQH K\GUD]LQ\O EHQ]R>d@WKLD]ROH ZHUH V\QWKHVL]HG ,Q RUGHU WR HQODUJH PROHFXODU GLSROH PRPHQW K\GUD]RQH ZDV GHVLJQHG DV D Œ FRQMXJDWLRQ FRUH WR UHSODFH SRO\HQHV ,W KDV EHHQ IRXQG WKDW ILYH PHPEHUHG KHWHURDURPDWLF ULQJV SURYLGH ODUJHU HQKDQFHPHQW RI PROHFXODU QRQOLQHDULW\ WKDQ SKHQ\O ULQJ EHQ]RWKLD]RO\O JURXS ZDV VHOHFWHG WR UHSODFH SKHQ\O ULQJ IROORZLQJ WKLV WKHRU\ 7R HVWLPDWH WKH LPSDFW RI Œ FRQMXJDWLRQ RQ WKH QRQOLQHDU DEVRUSWLRQ S\UHQ\O DQG GLPHWKR[\EHQ]HQH ZHUH LQWURGXFHG LQWR PROHFXOH $ DQG $

UHVSHFWLYHO\ 6LQFH S\UHQH EDVHG GHULYDWLYHV KDYH DEXQGDQW Œ HOHFWURQV DQG WKXV SRVVHVV ODUJH 73$

FURVV VHFWLRQ

EHWWHU 2/ SHUIRUPDQFH ZDV H[SHFWHG LQ $ FRPSRXQG

7KH PHFKDQLVP DQG FDSDELOLW\ RI 2/ ZHUH LQYHVWLJDWHG XQGHU GLIIHUHQW SXOVH ZLGWKV IRU ERWK FRPSRXQGV $ VKRZV VXSHULRU UHYHUVH VDWXUDEOH DEVRUSWLRQ DW PXOWL ZDYHOHQJWKV ZKLFK ZDV ODUJHO\ HQKDQFHG E\ WKH LQWURGXFLQJ RI S\UHQ\O $ WKUHH OHYHO PRGHO JURXQG VWDWH 6 H[FLWHG VWDWH 6 DQG KLJKHU H[FLWHG VWDWH 6 RQ

ACS Paragon Plus Environment

Page 5 of 34 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

WKH VLQJOHW VWDWH ZDV EXLOW WR H[SODLQ WKH G\QDPLF SURFHVV

2/ H[SHULPHQWV ZHUH FDUULHG RXW DQG WKH UHVXOWV

LQ WKLV ZRUN ZHUH FRPSDUHG ZLWK RWKHU 2/ PDWHULDOV $ GLVSOD\V XOWUDIDVW EURDGEDQG 2/ IURP YLVLEOH WR QHDU LQIUDUHG ZDYHOHQJWKV

a

QP DQG WKH PHDVXUHG 2/ WKUHVKROGV DUH VPDOOHU WKDQ PRVW RI

SUHYLRXVO\ UHSRUWHG PDWHULDOV LQGLFDWLQJ DQRWKHU VWHS WRZDUGV WKH DSSOLFDWLRQ RI XOWUDIDVW EURDGEDQG 2/

([SHULPHQWDO 0HWKRGV DQG 7KHRUHWLFDO &DOFXODWLRQ

6\QWKHVLV

6\QWKHVLV RI ( 7KH PL[WXUH RI

S\UHQ

\OPHWK\OHQH K\GUD]LQ\O EHQ]R>d@WKLD]ROH

K\GUD]LQREHQ]RWKLD]ROH

PPRO ZDV SODFHG LQ D

PJ

PPRO DQG

S\UHQHFDUER[DOGHK\GH

FF WKUHH QHFNHG URXQG ERWWRPHG IODVN $QK\GURXV HWKDQRO

PJ

PO ZDV DGGHG LQ

LW DQG WKH IODVN ZDV KHDWHG XQWLO WKH PL[WXUH GLVVROYHG FRPSOHWHO\ &RQFHQWUDWHG K\GURFKORULF DFLG GURSV DV WKH FDWDO\VW ZDV DGGHG LQ WKH UHDFWLRQ V\VWHP 7KH UHDFWLRQ WLPH LV DERXW

WR

KRXUV $IWHU FRROLQJ WR

URRP WHPSHUDWXUH WKH UHVLGXH ZDV ILOWHUHG XQGHU UHGXFHG SUHVVXUH 7KH ILOWHU FDNH ZDV ZDVKHG IRXU WLPHV ZLWK DQK\GURXV HWKDQRO DIWHU WKDW WKH FRPSRXQG $ 0+] '062 d P +]

+] + a

)LJXUH 6 6

+

G J GG J

W J

+] &

+] +]

+

+

W J

PJ

+

G J W J +]

&

&DOFG IRU & + 1 6 &

ZDV GULHG XQGHU YDFXXP + 105 / SSP +]

+]

+

+

+

G J V

+

06 (6, P ] +

G J

1

6

ACS Paragon Plus Environment

+]

+

+

& 105 / SSP >0 +@

6

+]

G J 0+] 6ROLG

6HH VXSSRUW LQIRUPDWLRQ

)RXQG &

+

1

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

7KH V\QWKHWLF URXWH RI WKH WDUJHW FRPSRXQG $ DQG $

6FKHPH 6\QWKHVLV RI ( 7KH PL[WXUH RI

Page 6 of 34

GLPHWKR[\EHQ]\OLGHQH K\GUD]LQ\O EHQ]R>d@WKLD]ROH K\GUD]LQREHQ]RWKLD]ROH

PPRO ZDV SODFHG LQ D

PJ

PPRO DQG

GLPHWK\O EHQ]DOGHK\GH

FF WKUHH QHFNHG URXQG ERWWRPHG IODVN $EVROXWH PHWKDQRO

PJ

PO ZDV DGGHG LQ

LW DQG WKH IODVN ZDV KHDWHG XQWLO WKH PL[WXUH GLVVROYHG FRPSOHWHO\ &RQFHQWUDWHG K\GURFKORULF DFLG GURSV DV WKH FDWDO\VW ZDV DGGHG LQ WKH UHDFWLRQ V\VWHP 7KH UHDFWLRQ WLPH LV DERXW

WR

KRXUV $IWHU FRROLQJ WR

URRP WHPSHUDWXUH WKH UHVLGXH ZDV ILOWHUHG XQGHU UHGXFHG SUHVVXUH 7KH ILOWHU FDNH ZDV ZDVKHG IRXU WLPHV ZLWK DEVROXWH PHWKDQRO DIWHU WKDW WKH FRPSRXQG $

PJ

/ SSP

V

0+] '062 d

a

W

+ J

105 / SSP a a & + 126 &

+]

a

V

+ 1+

W

+ J

+]

0+] 6ROLG &

+

a

a

G

P +

a

a

a

06 (6, P ] +

ZDV GULHG XQGHU YDFXXP + 105

>0 +@ 1

2

+ V

G +

a a

V a

a

6

)RXQG &

6

7UDQVLHQW 2SWLFDO 1RQOLQHDULW\

ACS Paragon Plus Environment

+

& &

a

6HH VXSSRUW LQIRUPDWLRQ )LJXUH 6 6

+

+

Ã

&DOFG IRU 1

2

Page 7 of 34 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 WUDQVLHQW DEVRUSWLRQ VSHFWUD ZHUH UHFRUGHG XQGHU WKH H[FLWDWLRQ RI

QP IV SXOVHV 7KH OLJKW VRXUFH ZDV

XVHG DQ RSWLFDO SDUDPHWULF DPSOLILHU 23$ /LJKW &RQYHUVLRQ 253+(86

IV

+] SXPSHG E\ D PRGH

ORFNHG

173$

H

FP *:

IV DFKLHYHG IURP

H

*0

FP *:

@

P

Hsræt

; :…• xäw{y wär{z sät{{ æ æ æ

: ; tuxäu syxäz u{ä{ æ æ æ

H

FP *: väyx zäyx rävxv æ æ æ

:H VXJJHVW WKDW K\GUD]RQH FDQ HQKDQFH WKH GRQDWLQJ FDSDELOLW\ RI SHULSKHUDO VXEVWLWXHQW LQ WKHVH DV\PPHWULF ^ FRQMXJDWLRQ V\VWHPV 0RUHRYHU H[WHQGLQJ ^ FRQMXJDWLRQ LQFUHDVHV WKH GHORFDOL]HG HOHFWURQV LQ WKH HOHFWURQ DFFHSWRU ZKLFK IXUWKHU HQKDQFH WKH LQWUDPROHFXODU FKDUJH WUDQVIHU $ GLVSOD\V VWURQJHU FKDUJH WUDQVIHU WKDQ $ XQGHU WKLV PHFKDQLVP DQG WKXV VKRZV ODUJHU 56$ )XUWKHUPRUH PROHFXODU QRQOLQHDU RSWLFDO UHVSRQVH FDQ EH ZHOO LPSURYHG E\ H[WHQGLQJ WKH ^ FRQMXJDWLRQ RI SHULSKHUDO VXEVWLWXHQW DOWKRXJK WKH ZKROH PROHFXOH LV QRW FRQMXJDWHG 6XFK HQKDQFHPHQW KDV EHHQ IRXQG LQ PDQ\ VLPLODU FRQMXJDWHG FRPSRXQGV FRQMXJDWHG OHQJWK RI SHULSKHUDO VXEVWLWXHQW LV HQODUJHG IURP $

WR $

7KH ^

S\UHQH JURXS KDV D ODUJHU ^

FRQMXJDWHG OHQJWK WKDQ GLPHWKR[\EHQ]HQH JURXS LW DOVR PDNHV FRQWULEXWLRQV WR WKH HQKDQFHPHQW RI 73$ ZKLFK LV UHSRUWHG PDQ\ WLPHV 8OWUDIDVW %URDGEDQG 2SWLFDO /LPLWLQJ $

GLVSOD\HG VWURQJHU EURDGEDQG 56$ XQGHU IHPWRVHFRQGV DQG SLFRVHFRQGV LQ = VFDQ H[SHULPHQWV

)XUWKHUPRUH $ KDV D KLJK WUDQVPLWWDQFH IURP YLVLEOH WR LQIUDUHG UHJLRQV 7KHVH PDNH $ D VXLWDEOH PDWHULDO IRU RSWLFDO OLPLWLQJ 7R HYDOXDWH WKH RSWLFDO OLPLWLQJ 2/ SURSHUW\ RI $ YDULRXV ZDYHOHQJWKV ,Q )LJXUH LUUDGLDQFH WKURXJK D

H[SHULPHQWV ZHUH FRQGXFWHG XQGHU

WKH YDULDWLRQV RI WKH WUDQVPLWWDQFH RI $ DV D IXQFWLRQ RI WKH ODVHU LQSXW

PP FXYHWWH IRU

QP

QP

QP

ACS Paragon Plus Environment

QP

QP DQG

QP $ VKRZV

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

KLJK OLQHDU WUDQVPLWWDQFH XQGHU DOO WKH ZDYHOHQJWKV

Page 16 of 34

a

7KH WUDQVPLWWDQFH RI $ VROXWLRQ GHFUHDVHV

ZLWK LQFUHDVLQJ LQSXW LUUDGLDQFH XQGHU PXOWL ZDYHOHQJWKV

IV H[FLWDWLRQ VKRZLQJ H[FHOOHQW EURDGEDQG

RSWLFDO OLPLWLQJ SHUIRUPDQFH IURP

QP WR

QP

7KH RSWLFDO OLPLWLQJ SHUIRUPDQFH RI $ LV EHWWHU WKDQ PRVW RI WKH 2/ PDWHULDOV WKDW KDYH EHHQ UHSRUWHG VXFK DV )H 2 QDQRFRPSRVLWH 6KRZQ LQ WKH 7DEOH

)LJXUH

RUJDQLF PROHFXODU QDQR PLFURFU\VWDOV

DQG VRPH S\UHQH EDVHG PROHFXOHV

LQGLFDWLQJ $ D SURPLVLQJ PDWHULDO IRU XOWUDIDVW EURDGEDQG RSWLFDO OLPLWLQJ

8OWUDIDVW RSWLFDO OLPLWLQJ RI $ DV D IXQFWLRQ RI WKH LQSXW LUUDGLDQFH DW QP QP DQG QP

7DEOH &RPSDULVRQ ZLWK WKH UHSRUWHG QRYHO RSWLFDO OLPLWLQJ PDWHULDOV WUDQVPLWWDQFH 6DPSOH

3XOVH

$

IV

)H 2 $J QDQRFRPSRVLWHV

IV

2UJDQLF 0ROHFXODU 1DQR 0LFURFU\VWDOV

IV

3\UHQH EDVHG PROHFXOHV

IV

QP

7

7KUHVKROG - FP

a

a

a

!

ACS Paragon Plus Environment

a

QP

7 UHSUHVHQWV WKH OLQHDU

:DYHOHQJWK QP

a

QP

5HI 7KLV ZRUN

Page 17 of 34 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

$ VKRZV H[FHOOHQW RSWLFDO OLPLWLQJ XQGHU IHPWRVHFRQGV SXOVH H[FLWDWLRQ 0HDQWLPH $ H[KLELWV UHODWLYHO\ ORQJ (6$ OLIHWLPH DERXW SLFRVHFRQGV DW

SV VR ZH IXUWKHU LQYHVWLJDWHG WKH 2/ SURSHUW\ XQGHU

QP 7KH UHSHWLWLRQ UDWH ZDV

+] WR HOLPLQDWH VSXULRXV FXPXODWLYH HIIHFWV

RULJLQDWHG IURP WKHUPDOO\ LQGXFHG QRQOLQHDULWLHV 6DPSOH VROXWLRQ ZDV FRQWDLQHG LQ

PP

TXDUW] FHOO 7KH YDULDWLRQ RI WKH WUDQVPLWWDQFH DV D IXQFWLRQ RI WKH LQFLGHQW LQWHQVLW\ ZDV VKRZQ LQ )LJXUH

$OO WKH WKUHVKROGV DUH VKRZHG LQ 7DEOH

)LJXUH

2SWLFDO OLPLWLQJ RI $ DV D IXQFWLRQ RI WKH LQSXW LUUDGLDQFH DW SLFRVHFRQGV

2QH FDQ IRXQG WKDW DOWKRXJK $ GLVSOD\V VDWXUDEOH DEVRUSWLRQ DW

QP a

QP XQGHU

QP LQ WKH

WUDQVLHQW DEVRUSWLRQ VSHFWUD RSWLFDO OLPLWLQJ FRXOG VWLOO EH UHDFKHG XQGHU WKHVH ZDYHOHQJWKV 7KH ODUJH 73$ DW

QP DQG

QP GRPLQDWH WKH QRQOLQHDU DEVRUSWLRQ DQG FRPSHQVDWH WKH

VDWXUDEOH (6$ 7KLV H[SDQGV RXU LGHDV RI GHVLJQLQJ VXSHULRU 2/ PDWHULDOV 73$ DQG (6$ DUH QRW VWULFWO\ UHTXLUHG WR EH ERWK HQKDQFHG WR UHDFK EURDGEDQG 2/ 7KH\ FDQ FRPSHQVDWH HDFK RWKHU ZLWK SURSHU GHVLJQ DQG UHVXOW LQ DQ H[WHQGHU 2/ EDQGZLGWK

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

7DEOH

Page 18 of 34

7KH 2/ WKUHVKROG RI $ DW PXOWL ZDYHOHQJWKV XQGHU IHPWRVHFRQGV DQG SLFRVHFRQGV

3XOVH ZLGWK

:DYHOHQJWK QP

7

7KUHVKROG - FP

H

IV

SV

&RQFOXVLRQV ,Q VXPPDU\ WZR QRYHO K\GUD]RQ GHULYDWLYHV ZHUH GHVLJQHG DQG V\QWKHVL]HG WR DFKLHYH XOWUDIDVW EURDGEDQG RSWLFDO OLPLWLQJ 7UDQVLHQW DEVRUSWLRQ VSHFWUD DQG = VFDQ H[SHULPHQWV LQGLFDWHG VLQJOHW EDVHG 73$ (6$ &RPSDUHG ZLWK $

$ VKRZHG D VXSHULRU EURDGEDQG 56$ DW PXOWL

ZDYHOHQJWKV IURP IHPWRVHFRQGV WR SLFRVHFRQGV 7KH VXSHULRU 1/2 UHVSRQVH RULJLQDWHG IURP WKH VWURQJHU LQWUDPROHFXODU FKDUJH WUDQVIHU DQG ODUJHU ^ FRQMXJDWHG V\VWHP LQ $ EURDGEDQG 2/ SHUIRUPDQFH UDQJH IURP

QP WR

6DWLVILHG XOWUDIDVW

QP ZDV VKRZHG XQGHU IHPWRVHFRQGV

DQG SLFRVHFRQGV 7KH VLPSOH V\QWKHVLV SURFHGXUH ORZ ORVW RXWVWDQGLQJ EURDGEDQG 1/2 SURSHUWLHV PDNH WKHVH GHULYDWLYHV SURPLVLQJ FDQGLGDWH IRU EURDGEDQG 2/ PDWHULDOV $662&,$7(' &217(17 6XSSRUWLQJ ,QIRUPDWLRQ s

•’‡…–”—•á D > /rdK& •‰ šŒµu v 6ROLG VWDWH & 105 VSHFWUXP }( í v

‰Œ • vš

X

•]

•U 7*$ GDWD RI $ DQG $ XQGHU QLWURJHQ DWPRVSKHUH DUH DOVR SUHVHQWHG

$87+25 ,1)250$7,21

ACS Paragon Plus Environment

î Œ

Page 19 of 34 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

&RUUHVSRQGLQJ $XWKRU ( PDLO \OVRQJ#KLW HGX FQ $&.12:/('*0(17 $XWKRUV JUDWHIXOO\ DFNQRZOHGJH WKH VXSSRUW RI WKH 16$) *UDQW 1R 8 1DWXUDO 6FLHQFH )RXQGDWLRQ RI &KLQD 1R 3URYLQFH &KLQD *UDQW 1R %.

1DWLRQDO

1DWXUDO 6FLHQFH )RXQGDWLRQ RI -LDQJVX DQG 1DWXUDO 6FLHQFH )RXQGDWLRQ RI WKH +LJKHU

(GXFDWLRQ ,QVWLWXWLRQV RI -LDQJVX 3URYLQFH &KLQD *UDQW 1R

.-%

5()(5(1&(6 +H * 6 7DQ / 6 =KHQJ 4 3UDVDG 3 1 0XOWLSKRWRQ DEVRUELQJ PDWHULDOV 0ROHFXODU GHVLJQV FKDUDFWHUL]DWLRQV DQG DSSOLFDWLRQV Chem. Rev &DOYHWH 0