Gas Adsorption Effects on the Electronic Properties ... - ACS Publications

Subscriber access provided by RMIT University Library

Article

Gas Adsorption Effects on the Electronic Properties of Two-dimensional Nickel Bis(Dithiolene) Complex Hongmei Liu, Xiaolong Li, Li Chen, Xiaoli Wang, Hongzhe Pan, Xiaoming Zhang, and Ming-Wen Zhao J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.5b11699 • Publication Date (Web): 01 Feb 2016 Downloaded from http://pubs.acs.org on February 4, 2016

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 C 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 30 24

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

*DV$GVRUSWLRQ(IIHFWVRQWKH(OHFWURQLF3URSHUWLHVRI

7ZR'LPHQVLRQDO1LFNHO%LVGLWKLROHQH &RPSOH[

+RQJPHL/LX ;LDRORQJ/L /L&KHQ ;LDROL:DQJ+RQJ]KH3DQ;LDRPLQJ =KDQJ0LQJZHQ=KDR

,QVWLWXWHRI&RQGHQVHG0DWWHU3K\VLFV/LQ\L8QLYHUVLW\/LQ\L6KDQGRQJ&KLQD 6FKRRORI3K\VLFVDQG6WDWH.H\/DERUDWRU\RI&U\VWDO0DWHULDOV6KDQGRQJ8QLYHUVLW\-LQDQ 6KDQGRQJ&KLQD

$EVWUDFW 7ZRGLPHQVLRQDO' PHWDORUJDQLFIUDPHZRUNV02)V DUHIXQFWLRQDOPDWHULDOVLQ HOHFWURQLFGHYLFHVGXHWRWKHWXQDEOHHOHFWURQLFSURSHUWLHV+HUHXVLQJILUVWSULQFLSOHV FDOFXODWLRQV ZH GHPRQVWUDWH WKDW WKH UHFHQWO\ V\QWKHVL]HG ʌFRQMXJDWHG QLFNHO ELVGLWKLROHQH FRPSOH[ ZLWK D FKHPLFDO IRUPXOD 1L&6 FDQ EH XVHG WR GHWHFW SRLVRQRXV JDVHV VXFK DV &2 DQG 12 PROHFXOHV 7KH DGVRUSWLRQV RI &2 DQG 12 PROHFXOHV RQ ' 1L&6 VXUIDFH OHDG WR D FKDQJH RI HOHFWURQLF VWUXFWXUH IURP VHPLFRQGXFWLQJ WR PHWDOOLF ZKLOH 2 FDQ¶W 7KH HOHFWURQLF VWUXFWXUH FKDQJH FDQ EH XQGHUVWRRGIURPWZRUHVSHFWVRZLQJWRWKHVWURQJLQWHUDFWLRQEHWZHHQ1LDWRPVDQG &2 RU 12 PROHFXOHV FKDUJH WUDQVIHUIURP WKHDGVRUEHG PROHFXOHV WR WKH QDQRVKHHW JLYHV ULVH WR D ODUJH XSZDUG VKLIW RI WKH )HUPL OHYHO DQG WKH VWURQJ RUELWDO K\EULGL]DWLRQ EHWZHHQ 1L G RUELWDOV DQG &2 V RU 12 S RUELWDOV SURYLGHV PRUH HOHFWURQLF VWDWHV DURXQG WKH )HUPL OHYHO 7KHVH UHVXOWV VXJJHVW WKH SRWHQWLDO DSSOLFDWLRQRI'02)VLQVHQVRUVDQGHOHFWURQLFGHYLFHV

ϭ

ACS Paragon Plus Environment


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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Ϯ


Page 2 of 30 24

Page 3 of 30 24

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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ϯ



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

3HUGHZí%XUNHí(UQ]HUKRI JHQHUDOL]HG JUDGLHQW DSSUR[LPDWLRQ XVLQJ WKH SODQH ZDYH EDVLV 9LHQQD DE LQLWLR VLPXODWLRQ SDFNDJH 9$63 *ULPPH¶V FRUUHFWLRQ ' LV DOVR DGRSWHG WR DFFRXQW IRU ZHDN YDQ GHU :DDOV LQWHUDFWLRQV ZLWKLQ WKH DGVRUEHG V\VWHPV$OORIWKHFDOFXODWLRQVDUHSHUIRUPHGZLWKDSODQHZDYHFXWRIIRIH9RQ WKHîî0RQNKRUVW3DFNNSRLQWPHVK7KHYDFXXPOD\HULVcWKLFNWRHQVXUH GHFRXSOLQJ EHWZHHQ QHLJKERULQJ VODEV 'XULQJ VWUXFWXUDO UHOD[DWLRQ DOO DWRPV DUH UHOD[HGXQWLOWKHWRWDOHQHUJ\FKDQJHLVOHVVWKDQH9DQGWKHIRUFHRQHDFKDWRPLV VPDOOHU WKDQ H9c )RU GHQVLW\ RI VWDWHV '26 FDOFXODWLRQV D WZLFH GHQVHU NSRLQWPHVKLVXVHG,QDGGLWLRQWKHVSLQSRODUL]HGFRPSXWDWLRQLVDOVRSHUIRUPHGWR H[DPLQHWKHLUPDJQHWLFSURSHUWLHV 5HVXOWVDQGGLVFXVVLRQV $GVRUSWLRQVWUXFWXUHHQHUJ\DQGPDJQHWLFFRQILJXUDWLRQV )LJXUH D VKRZV WKH RSWLPL]HG VWUXFWXUH RI ' 1L&6 QDQRVKHHW ZKLFK DGRSWVDNDJRPHODWWLFH7KHRSWLPL]HGODWWLFHFRQVWDQWLVIRXQGWREHD c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ϰ


Page 4 of 30 24

Page 5 of 30 24

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


SEDFNGRQDWLRQ2QWKHRWKHUKDQGDGVRUSWLRQRIERWK12DQG2RFFXUVLQDEHQG IDVKLRQ GXH WR WKH G]1L S 12 RU 2 RUELWDO LQWHUDFWLRQ ZLWK )H±1±2 DQG)H±2±2 DVOLVWHGLQ7DEOH7KLVEHQGLQJIDVKLRQLVVLPLODUWRWKHFDVH RI 12 RU 2 FRRUGLQDWHG ZLWK RWKHU PHWDORUJDQLF FRPSRXQGV VXFK DV LURQ,, SRUSK\ULQ )RU WKH ELQGLQJ VWUHQJWK &2 DQG 12 PROHFXOHV VKRZ FKHPLVRUSWLRQ ZLWK D VKRUW 1L& DQG 1L1 GLVWDQFH RI c DQG c UHVSHFWLYHO\ EXW 2 PROHFXOHVDUHSK\VLVRUEHGRQWKHDWRSVLWHRIWKH1LDWRPVZLWKDODUJH1L2GLVWDQFH RI c 7KH VWURQJ LQWHUDFWLRQ EHWZHHQ WKH 1L DWRPV DQG DGVRUEHG PROHFXOHV UHVXOWV LQ D GLVSODFHPHQW 'G RI 1L DWRPV DERYH WKH EHQ]HQH SODQH RI c DQG c IRU &2 DQG 12 UHVSHFWLYHO\ $V D UHVXOW WKH SODQDU VWUXFWXUH LV VOLJKWO\ GLVWRUWHGIRU&2DQG12DGVRUEHGV\VWHPVDVSUHVHQWHGLQWKHORZHUSDQHORI)LJE ,QFRQWUDVWWKHQDQRVKHHWUHPDLQVSODQDUDIWHUWKHDGVRUSWLRQRI2PROHFXOHVGXHWR WKHZHDNLQWHUDFWLRQ)LJG 7DEOH OLVWV WKH DGVRUSWLRQ HQHUJ\ (DGV RI SHU JDV PROHFXOH RQ 1L&6 VXUIDFH ZKLFK LV GHILQHG DV (DGV >(1L&6 (;2 ±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ϱ



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

DGVRUSWLRQVLQ)LJD7KHDGVRUSWLRQVRI12DQG2H[LVWDORFDOHQHUJ\PLQLPXPDW cDQGcUHVSHFWLYHO\+RZHYHUDV&2PROHFXOHVDSSURDFKWR1LDWRPVDQ HQHUJ\ EDUULHU DSSHDUV DURXQG c DQG WKHQ WKH WRWDO HQHUJ\ UHDFKHV WKH ORFDO PLQLPXPDWc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ϲ


Page 6 of 30 24

Page 7 of 30 24

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


IHUURPDJQHWLF FRQILJXUDWLRQ ZLWK D PDJQHWLF PRPHQW RI P% LV IRXQG WR EH WKH PRVW HQHUJHWLFDOO\ VWDEOH IRU WKH 2DGVRUEHG V\VWHP 6XFK IHUURPDJQHWLVP PDLQO\ DULVHV IURP WKH XQSDLUHG HOHFWURQV LQ 2 PROHFXOHV )LJXUH F SORWV WKH VSDWLDO GLVWULEXWLRQ RI VSLQSRODUL]HG HOHFWURQ GHQVLW\ ZKLFK LV FDOFXODWHG IURP WKH FKDUJH GHQVLW\ GLIIHUHQFH EHWZHHQ WKH VSLQXS DQG VSLQGRZQ FKDQQHOV 'U Un Up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ϳ



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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ϴ


Page 8 of 30 24

Page 9 of 30 24

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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ϵ



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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ϭϬ


Page 10 of 30 24

Page 11 of 30 24

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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±&+ ±1+DQG±2+JURXSV$OOWKHVHOLJDQGVVKRZVWURQJLQWHUDFWLRQZLWK1LDWRPVZLWK DELQGLQJGLVWDQFHLQWKHUDQJHRI±c7KH1L&6QDQRVKHHWDOVRWXUQVWR EH PHWDOOLF DV FRRUGLQDWHG ZLWK ±&+ ±1+ DQG ±2+ JURXSV 6HH )LJXUH 6 LQ ϭϭ



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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¶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ϭϮ


Page 12 of 30 24

Page 13 of 30 24

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


$662&,$7('&217(17 6XSSRUWLQJ,QIRUPDWLRQ 7KH 6XSSRUWLQJ ,QIRUPDWLRQ LV DYDLODEOH IUHH RI FKDUJH RQ WKH $&6 3XEOLFDWLRQV ZHEVLWHDW'2, %DQG VWUXFWXUH RI WKH &2 RU 12DGVRUEHG 1L&6 QDQRVKHHW ZLWK GLIIHUHQW DGVRUSWLRQFRYHUDJHDQGWKH1L&6QDQRVKHHWFRRUGLQDWHGZLWK±&+±1+DQG ±2+JURXSV $87+25,1)250$7,21 &RUUHVSRQGLQJ$XWKRUV

(PDLOOLXKRQJPHL#O\XHGXFQ 1RWHV 7KHDXWKRUVGHFODUHQRFRPSHWLQJILQDQFLDOLQWHUHVW $&.12:/('*0(176 :H WKDQN 3URI )HQJ /LX IRU YDOXDEOH GLVFXVVLRQV 7KLV ZRUN ZDV VXSSRUWHG E\ WKH 1DWLRQDO1DWXUDO6FLHQFH)RXQGDWLRQRI&KLQD1RV +/LXDFNQRZOHGJHVWKHVXSSRUWRI.H\'LVFLSOLQHRI&RQGHQVHG0DWWHU 3K\VLFV RI /LQ\L 8QLYHUVLW\ WKH 3URMHFW RI 2XWVWDQGLQJ

Gas Adsorption Effects on the Electronic Properties ... - ACS Publications

Recommend Documents