Molecular Ion Formation by Photoinduced Electron Transfer at the

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Letter

Molecular Ion Formation by Photo-Induced Electron Transfer at the Tetracyanoquinodimethane/Au(111) Interface David Gerbert, and Petra Tegeder J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.7b01897 • Publication Date (Web): 12 Sep 2017 Downloaded from http://pubs.acs.org on September 14, 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 Letters 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.

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The Journal of Physical Chemistry Letters

                     

        ∗                   !" #$% &   '       

    

                                                 

 !" ###    $          %         &           $      '        &    ()                     

*     $  &         $ 

           + 

           

     

        $ $     $                     &                  !" ###     $       &         $ , &     $        -       ()    

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hn

e-

     !! """  #$!  $ %" ! "&' ! "  "" $"(



)   *" "$$*  "+! +$"

%! +  !   "  * %" ," -  "$ $$"(   ."!"  " $ ! " ! !%$+ -  "$ $$"  $ + !!"'  !$! $*"" ! / -  $+* """  $$* !! " " !!  +/  -+ -   $ !%"(



 

0$$ !' +  ! ! %* +1

!" 2 ""% "( +' $$+ !" " "  * !  !" %  2 &  +1 +3"  "!"   !! """   +$"   $1 ! $$ " 4$!(

 

5&%' $* $$! #+$ !" ! &$$ !4! "+$" 

1$  %" -  -!+$  *"$ ! +$ """ " " - "  !!  "-  -"( ) " 6 & "!!   !!  "-   *7!+

89 :;  -( 89 " 3&  1 %$* !  %" +$ " -"



!  "  $ ,* EA < (= > "  +$  +$$ $

 "-' 1  "*" +" $3$* $  ;  (   ? $ +"*

?0 ! @ * $ ""* @ ? "!" ""  $* !!  &3 - &3$* !"1! 89 +$$"  ;  ' & " "1$/! 1* +$$ *! 1!"(     8%$""' !" " &$$ !4! +$$ !" + 

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*'  1!  - &3 - Φ %$"  -+ ( >  ( >  % 1 ! - " $ -( ;" " %$"  "! -   &!"  "  "- "  ;  &3 - Φ < ( > $"   +!!$ - "  ' & "  3*   $ ! " +%  + " "!* -  $ "  $  &3 - -  89:;   -( A" * "$%! &  +"" 

B & !+!  $

"' ((' ! ! ! $ "" " &$$ "  &3 - -  +$* 06 89  ;  (  " &$$ !4! !"1:"1" "*"+ & +"!  Φ - ( ± (  >'  %$ & $$* " "   "-  ( ?"$*' $$+  "+$ & A> " "$!  

Φ

"  

(±0.05 >' &$  !4! 89 !%! $ ""  C!( "  Φ

%$ """   "- * ( +$ % !"  %"

"" $!   $ Φ %$ -   $$+! "+$ ( ± (  > ( D ""  1"%! C" &  ((  $ "- -+  +$ "1"   89 +$$"'  % "( )  ! +$$"  $"  1! 1*  &3 $ 1(    "&"  B " - 06 89  ;  !! & !C  "(  * !!! +"+"  !!  ""  1"%!  +"" -"  !  ! $ "" - !$" " E-"(    (  &3 - - 06 89  ;  +"  ( ± (  > $& * C -  

B " ( ; -+  13! 1$& EF inal −EF < (  > EF  + *

" -+  $! ! 1!"' 4% +"" -"  1 1"%!( ; 

B 3

F" 1$&  + ! $!  ( ± ( > & "  B  1 ""!   "-! ;  "- " ??G (  "- " -  1 ;  "- " $!  ( >( "  !"1 !!   "- - Δ = 160 ± 30 +> " -! " $" 1!  " $ ""* ?? (   ;!  ;+1" 

) " "+$$ !"1 !!  "- -  "- "  1 ""! & =

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10 IPS m = 1.2 ± 0.2

a)

q = 1.0±0.1 ML

SS‘ m = 1.9 ± 0.1 EFinal - EF [eV]

2PPE Intensity [normalized]

9 8 7

UMO m = 1.2 ± 0.1 HOMO m = 2.0 ± 0.1

IPS1

FS m = 0.1 ± 0.2

6 4.0

4.2 4.4 4.6 4.8 Photon Energy [eV]

5.0

SS‘

5

6

b)

hn = 4.79 eV 4.61 eV 4.42 eV 4.30 eV 4.19 eV

UMO

s ure eat MO df an HO d-b FS + +

7 8 9 E Final - EF [eV]

10

2PPE Intensity [normalized]

q = 1.0±0.1 ML increasing hn = 4.75 eV photon dose IPS1 FS HOMO

es

tur

ea

df

an

d-b

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

5

6

SS‘ UMO

7 8 9 E Final - E F [eV]

10

    * !!  B " - 06 89:;  (  * #" %$"  4$ " * EF inal -  +! $" & "  EF EF inal − EF = Ekin + Φ "'  $& * C "!"   &3 -

Φ -  !"1:"1" "*"+( )"  * !! 3 ""  "" 3" 1"%!    B "+  !' ! +!  4$ $ ""( ; "$ -  """   3 " -+  ! "'  "$ - & " $!  3"  -+ ! ""' &$   * !! 3 " "$" -+ ! 4$ ""' $! 1%  %+ $%$( % +"" -" &  1 ""!   50'  "-! ?3$* "- " ??G '  ! +$$ !! $ " A0 '  4" + $ " ) ?1 !  4$ " ?  1"%!( 1 A> $ #" -  06 89  ;  $!"   &3 - "(



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 -$ +$ +$$ !" - 1 =( H' & + 1  ! -  "+$$ -$ &% - %$' $& +$:+$$ " !  "4  "-   89:;  -( ) !!'  +"" -   -+  ! "  1 ""!   " ! +$$ 1$

50 ( )"  " " (± (  > 1$& BF ( "'  / $

) " (± ( >  + & $ %$"(



0%' & ! $

 ""  1"%!    *  C - 

B "(  +""

-  1 ""!   ! +$$ !%! $ " A0 ( ) " $$* $!  =(± (  > 1% BF ! + " -+   $*  ! +$$ 1$ - 89( ; "! +"" -  1 ""!   4" + $ " ) ?1 $$* $!  −0.75 ± 0.05 > & "  B ( ;$ "$%!  B "&"  $ !"" -  ) ? !  "& (   * !!  B -  1 ""! &  ! 4$ " ? $$* $!  5.72 ± 0.05 > 1% B ( 8  

B  $" 1 !

$ "" 1%  %+ $%$( *  1 %&! "  " " %  &   #! $ "!" "$*   +$$ "' -$$&! 1* !+ ! !( A"  &!  - !C  " & !  1"% - +"" -"   * !+ &  $&" ! +$$ 1$ 6A0 - 89 " #!' & " ( > & " 

EF

"

!+! & ??(   " + 1 !   &3 &% - %$ " !$ ++ ( )$$+  "+$ &



< ( >   "+$ + - I $!" 

! "   &3 -( ;" "&  (  1

Φ

"" & "

 !" -+ ( ± (  >    " $+ - (± (  >( "'   -  +> " -! !  %$ & % #!"

Φ

-  1 ;  "-( 8

  &3 - %$ -!  - $$+ "!"   %$ -  06 89:;  !+! 1* $%$ +"" A ? "!" 3& -+ 

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q = 1.0±0.1 ML hn = 4.52 eV

2PPE Intensity [normalized]

a)

IPS1+SS‘

before illumination (F B ) after illumination (FA ) increasing annealing temperature (FC (T))

s ture fea FS + and d-b OMO +H UMO

5

6

7 8 E Final - E F [eV]

9

b) ln[ln(FB -FA )-ln(FC (T)-FA )]

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

0 -2 -4 -6

q = 1.0±0.1 ML hn = 4.52 eV EA= 43±11 meV

-8 4

6 8 -3 -1 1/T [10 K ]

10

    !! "$ +!4"   B "   89:;  -  1 %"! 1*  +$$* %! ""( 1 ;" $ -  +$  "$ -+  "" "&   ( ; +" -  &3 - 

" # - !$" " $! %  %" $ +( 5 Φ " "  "! &3 - - $$+' Φ ""  &3 - 1- $$+ ! Φ (T ) !"  &3 - - $ $ ""( $(  1%"$*' "

Φ

%$ "!"   89:;  "+$' & "

1 +!4! 1*  $$* !! ""( J   Φ  $"  +"" - " -+  ) ? "-" " ) ?"  !   %+ $%$( ) !!'  ??G " 7! & "  !"( )+$*' $$ 89 !%! 

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+"" -"   2! 1*  $ #"' ((' *     ""   "*( +'  & - "   " "  "$ - $$+( )"  "1" + $!"   Φ !" "  1 "  (   ( 1*  -$$* %"1$ "" " !4! - ", $'

*)  Φ %$ -   $$+! "+$ " 1!( ) !    7% "   % 1 %  +$$* !! 13 ' & "!!  "   &3 - ! $ - 10 +  $ +"  -+ 100 I  325 I(  % * EA " !+! -+  $% Φ ( A"  &3 - ΦC (T )' & !!"   $ + ' "  +" -  "" -  13  $% +1 - +$$" & & 13   $ ""' ((' 1- $$+ ' ΦA ! ΦB  &3 - - ! 1- $$+' "%$*' & 1  -$$& #"" ln[ln(ΦB − ΦA ) − ln(ΦC (T ) − ΦA )] = EA /kB T + const.



 &3 - %$" -  $ "' ΦC (T )'  "&   -+ - 7  "  - -  %" +  (  1 ' *$!  % * -  +$$* !! "" - EA < =± +>( ; !""" 1  % * &$$ 1 % 1$&(  = "++/"  1"%! %"1$ ""   06 89:;  ' (('   !! &3 - "- !  +$$* %! 13 ' & 1 %  2    "" -  +$$ $ ""( 8&' & %  !""" ""1$ !$* """ -  1"%! +( 1*' "%$  """  1 "!!   !""  +$ '   !"'    !! "$  + -  !"1' ! %  $$* !! -$  "-( ? & !  1"% * "    "   "* -  1"%! +"" - !  $$+' & #$!  

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DF 0.30 = eV

5.72 eV

4.45 eV

F = 5.50 eV

E i -EF

EVac

3.71 eV

FS

= DF eV 5 6 -0. 5.10 eV 1 IPS UMO

hn kBT

EF

EBind -EF

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

SS

-0.26 eV

SS’

HOMO -2.48 eV

Au(111)

1 ML TCNQ

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 $*/  !! $ "-  + !$' & 74!   "" ! -+!  !" !  * !! +"+"( ;" -  +$$* %! ' & "!  &3 - -  "+$ "  7% 1+3 -  "" -   "+$! (  Φ  "  - -  !" " !! #+$$* - - !C  "  (  (  &3 - " "  - -  !" np ' +1 - " -$$&"  "*+ 1% & ""  Φ = 5.20 ± 0.05 > ! ""   " %$ - Φ = 5.85 ± 0.05 >( )  1 4! 1*  "+$ + #$ " - Φ = Φ + ΔΦ exp( σ · np )



& " "!  !+  C% "" " σ( 8  -  " 1% ( > %  &3 - %$" - ! >  -!' (('  &3 - +"! - hν < ( > !"  "  ( > " (   ( )- "  "" &"  -$$* %"1$' & & 1  !"" "( 5&%'  "" " "" & "  * $"  10−21 +2 -  "   ( >( A"  1! %* -  "  !+ "" "" -   $$&" "  !& $"" 1  !$* # ""(   1 !"$*" "  * !! -  "" ""(   " $  4.25 ± 0.05 >   " !  "" " #1"  #$$* " ,* & "  *(  +"'   06 489:;   !! &3 - "- "  1"%!( E!  -$  !! $ "-'   " -  %$%! +$$ " "  1   %* -

4.25 ± 0.05 >

1%

EF (

A-$*' & !  1"%  89 !%!

$ "  " * ( ;" -  $ "  -+  6A0

" 1% '   1"% - +$$ $ ""   B + 1 !   %" &% - %$( 5&%'  #$$* " "" " &

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Work Function [eV]

a) 5.8 TCNQ/Au(111) q = 1.0±0.1 ML

5.6

hn = 4.42 eV -23 2 s = 5.5±0.2 10 cm hn = 4.52 eV -22 2 s = 1.2±0.1 10 cm hn = 4.79 eV -22 2 s = 8.8±0.1 10 cm hn = 4.86 eV -22 2 s = 7.7±0.2 10 cm

5.4 5.2 0

2 4 6 22 -2 Photon Dose [10 cm ]

b) 10 Cross Section [10-22cm2 ]

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

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8 6

TCNQ/Au(111) q = 1.0±0.1 ML F4TCNQ/Au(111) q = 1.0±0.1 ML

4 2 0 2.5 3.0 3.5 4.0 4.5 5.0 Photon Energy [eV]

   D3 -  & "  !" ! $$+ 4! &  #$ - !  7   !+ C% "" ""

σ ( 1  * !! -  C% "" "" -  06 89:;  (  +"   !! C " -! -  06 489:;  ( "  * " &!"  $ -  +$$ " 1*  $"    " ""(   $ &$! 1 - "  ! +$$ " (( 50  6A0   "1" +!! ! ""'  & (( $" -+  $! "- " "$* $  ! +$$ "(    !' & "  *  $ -  $"' &  " &  ! +$$ $%$ $! ! ( >' "$! 

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The Journal of Physical Chemistry Letters

" $$* ! "  11$* -  -+ -  %  "$! 1 !( ; 489:;  -  +$$"  $!* %$* ! - !"'    - $ "- "  -"1$( ;" "+$$* "&  "+ ' & ""  -$$& """  1 ""1$ -  %"1$ &3 - "   89:;  - 6 #" &  " - hν>( > $!"   $ $ -  ! +$$ " %  $ "- -+  +$$ "1"( ; $& +"  ! % "  "1$ ! +" $3$* !$! -+  "1" "  13 "- - $" " """!( 8   $ - 

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1*  "+$$ $ 1' &  1  - EA < =±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E hn > 4.25 eV

hot e -

EA 4.25 eV

EF

Au(111)

TCNQ

?+  "! "   89:;  - $!  %"1$ &3 - "( 5 $ !! ! "- -+  +$$ "1"   ! +$$ " !  +$$* %! 13 "- -  $"(

    "+$  89 +$$" & %! -+  C" $$ $!   + - 390 I ! !"!   ;  "$ *"$ $!  + + & &" %"$* $! 1* "%$ " ;+ '  + + !  $ *$"  800 I' 30 + ( J4! +$* % &" "! 1*  ", !" + !  "1"7 $ "  370 I' & $!"   !" - +$ $*" "  1 -$$&! 1* + ++! !"  J " " -+ ( ?+$  " &$$ "  J !    $ %+ +1   1" "" -

B #+" & -+!

5.3 · 10−11 +1(

 & 

+""  B #+" & -+!  $7!  + "  " & &" #$$* !"1! $"&(    ) !  "+$-*  +" - 

B " 3  !C  "  "  !"$*! "  -

- 4$ " * 1%  + $%$ B

= 0 '

B  − B

=

B − Φ( "

" "  &3 - Φ "!"    " -  "!* ! $& *  C ( $$*'  B $$&"  %" - 1' ! " 

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&$$ " ! $ ""(  "% ""+ &" %! 1* "!*   * !! -   " - !$" " E-"(    ) !  %  $ " -  $$+! 89:;  -' 

B +

"+" & -+! &  $$+ + - 10 "   -+$* $$+! "( ? $$! $$+ "" & 3 "  "1"7 "" -  " $"  B +"+"'  !  1 1$  "$% $$ "$ -"'   "+ " $ " -  &3 - %$ &" !(  $" " 4$ &" /! 1*  J + $!   " "!  A5> +1' & " 7%$   "+$ " " "/   ! - 150 μ+2 (   & -  $" 1+ &" "   "%$ D:+2' !!    *( I&  $" " "/ ! & $$&" -  $$ -  !  !" - * $$+ +(

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  ! 1*  + E" ! J   $$1% "  ?.  F . " -$$* 3&$!!( J(( 3&$!" 4$ " -+  5!$1 ! ?$ - !+$ *""(



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=

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 E1$' )(K .3' .( ;(K I+' ( >( ?$ D$$! 1 81 !? 8+ "" " 6 5%" ;""+1$"

!!  "- )"(

-) . ) ' %/' M =(

= 6+' >(K ?$' 0(K .$F' J(K .N!"' L( 6(K $' L( !!   ! E+1 J*+"  0!$ J:; " -  ?$ $$ ;$" ; $$ 9+ +$ +( 0) -) ) +() ' % /' M  (

 I' 6( B(K 6' I(K ' ( I(K ;$$!-' 0(K > J*' E( (K 5' L( ( 0$M +&3 0$" " +$ ?""( ) )  ' %% '  M(

 !' ( $$* ! +$$* )!! 0$$ ?& """  0$ ?-"( 0)  )1 ( ) .   ' 2' =  (

1' ;( (K D' ?( (K )%' L( (K ;%"' ;( L(K ."' L( (K ?! !' L( (K /*1&"3' .( ;(  ?&" - ?-" ! J%"( -) . )  '

!' ==M=(

 J6+' J( 0( +(( .  3( +(  (((    K ?'   K   M (

 "' ?( E(    A17" ! 6& "  B$ ;$"  $"(   ' 2 ,' M (

?%' E( ( $3 ." - $" ?$ $$"( +  ' "" '  =M =(

 ' 0( ;(K B+*' I(K 5"3&' O(K D' D(K J$' B( J(K 6%' J( 5(K 5 .$$' ;( D( ?$ $$ B,* 1$" %"  ( (

 (((   1

    -  (  ' !' =M=( 

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The Journal of Physical Chemistry Letters

 ;!+"' J( 0(K ."' 6(K !"*' ( B(K ' ?(K /' (K I' ( E(K I +' ( >(K 61+' 0(K 6!"*' ?(K 0"' E( ;(K  $('  "-   8"$  ?"( 0  ) ) 4 ' %&/'

M

(

 6!"+' ( J(K P' @( O( !! B$ "-  0$$ 0$ ) -"( ) )  ' %&#' M= (

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The Journal of Physical Chemistry Letters

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