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Ostwald ripening growth mechanism of gold nanotriangles in vesicular template phases Ferenc Liebig, Andreas F. Thunemann, and Joachim Koetz Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.6b02662 • Publication Date (Web): 03 Oct 2016 Downloaded from http://pubs.acs.org on October 5, 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.
Langmuir 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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Time dependent formation of nanotriangles 148x107mm (96 x 96 DPI)
ACS Paragon Plus Environment
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•–™ƒŽ† ”‹’‡•‹•‰ ‰”‘™–Š •‡…Šƒ•‹•• ‘ˆ ‰‘Ž† •ƒ•‘–”‹ƒ•‰Ž‡• ‹• ˜‡•‹…—Žƒ” –‡•’Žƒ–‡ ’Šƒ•‡• ‡”‡•… ‹‡„‹‰áS •†”‡ƒ• ä Šò•‡•ƒ••á½ ‘ƒ…Š‹• ‘‡–œS S ••–‹–—– ˆò” svvyx ‘–•†ƒ• ½
Š‡•‹‡á
•‹˜‡”•‹–¡–
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ƒ—• twá
‘Ž• á ‡”•ƒ•›
—•†‡•ƒ••–ƒŽ– ˆò”
ƒ–‡”‹ƒŽˆ‘”•…Š—•‰ —•† æ’”òˆ—•‰á
‘Ž›•‡”‡ ‹•
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ƒ•‘–‡…Š•‘Ž‘‰‹‡á •–‡” †‡• ‹…Š‡• zyá sttrw ‡”Ž‹•á ‡”•ƒ•›
ã Š‡ •‡…Šƒ•‹•• ‘ˆ •ƒ•‘–”‹ƒ•‰Ž‡ ˆ‘”•ƒ–‹‘• ‹• •—Ž–‹˜‡•‹…—Žƒ” ˜‡•‹…Ž‡• ‹• ‹•˜‡•–‹‰ƒ–‡† „› —•‹•‰ –‹•‡ †‡’‡•†‡•–
•‡ƒ•—”‡•‡•–• ‹• …‘•„‹•ƒ–‹‘• ™‹–Š
昋•
•’‡…–”‘•…‘’›á Ž‹‰Š– ƒ•† –”ƒ•••‹••‹‘• ‡Ž‡…–”‘• •‹…”‘•…‘’›ä • –Š‡ ˆ‹”•– –‹•‡ ’‡”‹‘† xäw •• •‹œ‡† •’Š‡”‹…ƒŽ ‰‘Ž† •ƒ•‘’ƒ”–‹…Ž‡• ƒ”‡ ˆ‘”•‡† ‹••‹†‡ ‘ˆ –Š‡ ˜‡•‹…Ž‡•á ™Š‹…Š „—‹Ž† —’ •‘ˆ– •ƒ•‘’ƒ”–‹…Ž‡ ƒ‰‰”‡‰ƒ–‡•ä • •‹–—
‡š’‡”‹•‡•–• •Š‘™ ƒ Ž‹•‡ƒ” ‹•…”‡ƒ•‡ ‘ˆ –Š‡
˜‘Ž—•‡ ƒ•† •‘Žƒ” •ƒ•• ‘ˆ •ƒ•‘–”‹ƒ•‰Ž‡• ‹• –Š‡ •‡…‘•† –‹•‡ ’‡”‹‘†ä Š‡ ˜‘Ž—•‡ ‰”‘™–Š ”ƒ–‡ ‘ˆ –Š‡ –”‹ƒ•‰Ž‡• ‹• sxäs ••u •‹• ƒ•† –Š‡ ‰”‘™–Š ”ƒ–‡ ‹• ˜‡”–‹…ƒŽ †‹”‡…–‹‘• ‘•Ž› rärt •• •‹•ä Š‡”‡ˆ‘”‡á ˆŽƒ– •ƒ•‘–”‹ƒ•‰Ž‡• ™‹–Š ƒ –Š‹…••‡•• ‘ˆ y •• ƒ•† †‹ƒ•‡–‡”• ‘ˆ tu •• ƒ”‡ ˆ‘”•‡†ä Š‹• ’”‘…‡•• …ƒ• „‡ †‡•…”‹„‡† „› ƒ †‹ˆˆ—•‹‘•æŽ‹•‹–‡† •–™ƒŽ† ”‹’‡•‹•‰ ‰”‘™–Š •‡…Šƒ•‹••ä
•‹…”‘‰”ƒ’Š• ˜‹•—ƒŽ‹œ‡ •‘ˆ– …‘”ƒŽæŽ‹•‡ •–”—…–—”‡• ™‹–Š –Š‹•
•ƒ•‘’Žƒ–‡Ž‡–• ƒ– –Š‡ ’‡”‹’Š‡”› ‘ˆ –Š‡ ƒ‰‰”‡‰ƒ–‡•á ™Š‹…Š †‹•ƒ‰‰”‡‰ƒ–‡ ‹• –Š‡ –Š‹”† –‹•‡ ’‡”‹‘† ‹•–‘ •ƒ•‘–”‹ƒ•‰Ž‡• ƒ•† •’Š‡”‹…ƒŽ ’ƒ”–‹…Ž‡•ä
Š‡ sx –‹•‡• ˆƒ•–‡” ‰”‘™–Š ‘ˆ
•ƒ•‘–”‹ƒ•‰Ž‡• ‹• Žƒ–‡”ƒŽ –Šƒ• –Šƒ– ‹• ˜‡”–‹…ƒŽ †‹”‡…–‹‘• ‹• ”‡Žƒ–‡† –‘ –Š‡ ƒ†•‘”’–‹‘• ‘ˆ •›••‡–”› „”‡ƒ•‹•‰ …‘•’‘•‡•–•á ‹ä‡äá
ƒ•† –Š‡ ’‘Ž›ƒ•’Š‘Ž›–‡ ƒŽ Š ‹• ƒ”„á ‘• –Š‡
sss ˆƒ…‡–• ‘ˆ –Š‡ ‰‘Ž† •ƒ•‘’Žƒ–‡Ž‡–• ‹• …‘•„‹•ƒ–‹‘• ™‹–Š …‘•ˆ‹•‡•‡•– ‡ˆˆ‡…–• ‘ˆ –Š‡ ˜‡•‹…—Žƒ” –‡•’Žƒ–‡ ’Šƒ•‡ä
‘””‡•’‘•†‹•‰ ƒ—–Š‘”ã ‘ƒ…Š‹• ‘‡–œ 敃‹Žã •‘‡–œ7—•‹æ’‘–•†ƒ•ä†‡ Š‘•‡ã ªv{ uus {yy wttr
‡›™‘”†•ã ‡š’‡”‹•‡•–•á
‘Ž† •ƒ•‘–”‹ƒ•‰Ž‡•á ‰”‘™–Š •‡…Šƒ•‹••á
•–™ƒŽ† ”‹’‡•‹•‰á ‹• •‹–—
á •‘ˆ– …‘”ƒŽæŽ‹•‡ ƒ‰‰”‡‰ƒ–‡• ACS Paragon Plus Environment
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sä •›••‡–”‹… •Šƒ’‡† ‰‘Ž† •ƒ•‘…”›•–ƒŽ• ƒ”‡ ‘ˆ ‹•…”‡ƒ•‹•‰ ‹•–‡”‡•– †—‡ –‘ –Š‡‹” •Šƒ’‡ †‡’‡•†‡•– ‘’–‹…ƒŽ ’”‘’‡”–‹‡•äsæu
‡…‡•–Ž›á ™‡ Šƒ˜‡ •Š‘™• ’”‘•‹•‹•‰ ”‡•—Ž–• ‘ˆ ‰‘Ž†
•ƒ•‘–”‹ƒ•‰Ž‡• ‹• •—”ˆƒ…‡æ‡•Šƒ•…‡† ƒ•ƒ• •…ƒ––‡”‹•‰áv ‹• ‰‘‘† ƒ‰”‡‡•‡•– ™‹–Š ‡ƒ”Ž‹‡” ’—„Ž‹•Š‡† †ƒ–ƒ ˆ”‘•
…ƒ”ƒ„‡ŽŽ‹ ‡– ƒŽäw
Ž‘•‰‹–—†‹•ƒŽ ƒ„•‘”’–‹‘• „ƒ•† ‹• –Š‡
Žƒ– •ƒ•‘–”‹ƒ•‰Ž‡• ‡šŠ‹„‹– ƒ •‘”‡ ‹•–‡••‹˜‡
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”‡‰‹‘• …ƒ• „‡ –—•‡† „› …‘•–”‘ŽŽ‹•‰ –Š‡ •‹œ‡ ƒ•† –Š‹…••‡•• ‘ˆ –Š‡
‹•†‹˜‹†—ƒŽ •ƒ•‘–”‹ƒ•‰Ž‡•áyáz ™Š‹…Š ‹• ‘ˆ •ƒŒ‘” „‹‘Ž‘‰‹… ‹•’‘”–ƒ•…‡ ˆ‘” ‹•ƒ‰‹•‰ ƒ’’Ž‹…ƒ–‹‘•• ‹• –‹••—‡á{ ‘” Š›’‡”–Š‡”•‹ƒ ‘ˆ …ƒ•…‡” …‡ŽŽ•äsr •Ž‹•‡ ‹• –Š‡ …ƒ•‡ ‘ˆ ƒ•‹•‘–”‘’‹… ‰‘Ž† •ƒ•‘”‘†• ™Š‡”‡ –Š‡ •‡‡†æ•‡†‹ƒ–‡† •›•–Š‡•‹• ‹• •ƒ‹•Ž› ƒ……‡’–‡†ásáuássást –Š‡ •‡…Šƒ•‹•• ‘ˆ •ƒ•‘–”‹ƒ•‰Ž‡ ˆ‘”•ƒ–‹‘• ‹• —•†‡” †‡„ƒ–‡ä Š‡ ‰”‘™–Š ‘ˆ ˜‡”› ••ƒŽŽá ’”‡ˆ‘”•‡† •’Š‡”‹…ƒŽ ‰‘Ž† •‡‡†• ‹•–‘ ƒ•‹•‘–”‘’‹… •ƒ•‘’ƒ”–‹…Ž‡• ”‡“—‹”‡• •›••‡–”›æ„”‡ƒ•‹•‰ …‘•’‘•‡•–•á ‡ä‰äá …ƒ–‹‘•‹… •—”ˆƒ…–ƒ•–• Ž‹•‡
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‘™‡˜‡”á –Š‡ ƒ•‹•‘–”‘’‹… •ƒ•‘…”›•–ƒŽ ‰”‘™–Š …ƒ• „‡ ‹•ˆŽ—‡•…‡† „› ƒ •’‡…‹ˆ‹… ƒ††‹–‹‘• ‘ˆ ŠƒŽ‹†‡ ‹‘••ásvásw ‘” „› …Šƒ•‰‹•‰ –Š‡ •‹•‡–‹… …‘•†‹–‹‘••äsx Š‡”‡ˆ‘”‡á –Š‡ …”›•–ƒŽŽ‹œƒ–‹‘• ’”‘…‡•• …ƒ• Ž‡ƒ† –‘ ”‘†æ•Šƒ’‡† ‘” ’Žƒ–‡Ž‡– •–”—…–—”‡•ä – ƒ •Ž‘™ ”‡ƒ…–‹‘• ”ƒ–‡ ‹• ’”‡•‡•…‡ ‘ˆ ‹‘†‹†‡ ‹‘•• ’”‡†‘•‹•ƒ•–Ž› •ƒ•‘–”‹ƒ•‰Ž‡• ƒ”‡ ˆ‘”•‡† ‹• •—…Š •‡‡†æ•‡†‹ƒ–‡† •›•–Š‡•‹•äsx —”–Š‡”•‘”‡á ‰‘Ž† •ƒ•‘–”‹ƒ•‰Ž‡• …ƒ• „‡ •›•–Š‡•‹œ‡† „› ƒ††‹•‰ •Šƒ’‡ …‘•–”‘ŽŽ‹•‰ ƒ‰‡•–•á ‡ä‰äá Ž‡•‘• ‰”ƒ•• ‡š–”ƒ…–•t ‘” –”›’–‘’Šƒ•syá ƒ• ™‡ŽŽ ƒ• ‹• –‡•’Žƒ–‡ ’Šƒ•‡•á ‡ä‰äá †‡•†”‹•‡”• ‘” „Ž‘…• …‘’‘Ž›•‡” •‹…‡ŽŽ‡• …ƒ• –ƒ•‡ ‘˜‡” –Š‹• ”‘Ž‡äszás{
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ƒ•’Š‹’Š‹Ž‹… „Ž‘…• …‘’‘Ž›•‡” •‹…‡ŽŽ‡• ƒ• –‡•’Žƒ–‡• –‘ †‹”‡…– –Š‡ ˆ‘”•ƒ–‹‘• ‘ˆ –”‹ƒ•‰—Žƒ” — Žt ’”‹•••äs{
Š‡ ‘”‹‡•–‡† •‹•‡”ƒŽ‹œƒ–‹‘• ’”‘…‡•• ‘ˆ
— Žt •ƒ•‘–”‹ƒ•‰Ž‡• ‹• •—…Š
–‡•’Žƒ–‡ ’Šƒ•‡• ‹• †‹•…—••‡† –Š”‘—‰Š –Š‡ •’ƒ–‹ƒŽ …‘•ˆ‹•‡•‡•– ˆ”‘• „Ž‘…•æ…‘’‘Ž›•‡” •‹…‡ŽŽ‡•ä —” ‘™• ”‡•‡ƒ”…Š ƒ…–‹˜‹–‹‡• ‹• –Š‹• ˆ‹‡Ž† ™‡”‡ ˆ‘…—•‡† ‘• –Š‡ ‘•‡æ•–‡’ •›•–Š‡•‹• ‘ˆ •ƒ•‘–”‹ƒ•‰Ž‡• ‹• ’”‡•‡•…‡ ‘ˆ ˜‡•‹…Ž‡•ä ’”‡•‡•…‡ ‘ˆ •‹š‡† ƒ”‡ ˆ‘”•‡†ätr
‘„‡”–•‘• ‡– ƒŽä Šƒ˜‡ ƒŽ”‡ƒ†› ‘„•‡”˜‡† –Šƒ– ‹•
’Š‘•’Š‘Ž‹’‹† ˜‡•‹…Ž‡• ‡š–”ƒæŽ‘•‰ •ƒ•‘”‘†• ƒ•† •ƒ•‘–”‹ƒ•‰Ž‡•
Š‡ ƒ•‘—•– ‘ˆ •ƒ•‘–”‹ƒ•‰Ž‡• …ƒ• „‡ ‹•…”‡ƒ•‡† „› ƒ††‹•‰ ƒ •ƒŽ–‘•‡æ
•‘†‹ˆ‹‡† ’‘Ž›‡–Š›Ž‡•‡‹•‹•‡
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‡…‡•–Ž› ’‡”ˆ‘”•‡† ‡š’‡”‹•‡•–• ™‹–Š
’Š‘•’Š‘Ž‹’‹† „ƒ•‡† ˜‡•‹…Ž‡• ‹• ’”‡•‡•…‡ ‘ˆ ƒ ’‘Ž›ƒ•’Š‘Ž›–‡á ‹ä‡äá ƒŽ Š ‹• ƒ”„á •Š‘™ –Šƒ– —•†‡” ‘’–‹•‹œ‡† …‘•†‹–‹‘•• –Š‡ ƒ•‘—•– ‘ˆ ƒ•‹•‘–”‘’‹… ’ƒ”–‹…Ž‡• …ƒ• ›‹‡Ž† xr¨á ƒ•† –Š‡ …‘””‡•’‘•†‹•‰ ƒ•‘—•– ‘ˆ •ƒ•‘–”‹ƒ•‰Ž‡• ur¨äváy ACS Paragon Plus Environment
‘–‡™‘”–Š›á ƒŽ•‘ –Š‡ •‡‡†æ
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•‡†‹ƒ–‡† •›•–Š‡•‹• Ž‡ƒ†• ‘•Ž› –‘ ƒ •Šƒ’‡ ›‹‡Ž† ‘ˆ •ƒ•‘–”‹ƒ•‰Ž‡• ‘ˆ ƒ„‘—– wr¨äw Š‡”‡ˆ‘”‡á ‹• ƒŽŽ …ƒ•‡• ƒ• ƒ††‹–‹‘•ƒŽ •‡’ƒ”ƒ–‹‘• •–‡’á ‡ä‰äá †‡’Ž‡–‹‘• ˆŽ‘……—Žƒ–‹‘•á ‹• •‡…‡••ƒ”› –‘ ‹•‘Žƒ–‡ ƒ•† ’—”‹ˆ› ‰‘Ž† •ƒ•‘–”‹ƒ•‰Ž‡•äváw • –Š‡ ’”‡•‡•– ™‘”• ™‡ ’‡”ˆ‘”•‡† –‹•‡ †‡’‡•†‡•– ‡š’‡”‹•‡•–• –‘ ‹•˜‡•–‹‰ƒ–‡ –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡ ˆ‘”•ƒ–‹‘• ’”‘…‡•• ‹• ’”‡•‡•…‡ ‘ˆ –Š‡ ˜‡•‹…—Žƒ” –‡•’Žƒ–‡ ’Šƒ•‡ä
á –”ƒ•••‹••‹‘• ‡Ž‡…–”‘• •‹…”‘•…‘’›
•’‡…–”‘•…‘’›á Ž‹‰Š– •‹…”‘•…‘’› …‘•„‹•ƒ–‹‘• ™‹–Š
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› —•‹•‰ †‹ˆˆ‡”‡•– •‡–Š‘†•á ‹ä‡äá
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–‹•‡ •…ƒŽ‡ä Š‡ •ƒ•‘’ƒ”–‹…Ž‡ ˆ‘”•ƒ–‹‘• ’”‘…‡•• …ƒ• „‡ †‹˜‹†‡† ‹•–‘ –Š”‡‡ ’‡”‹‘†•ä – ˆ‹”•– ‘•Ž› •’Š‡”‹…ƒŽ ’ƒ”–‹…Ž‡• ƒ”‡ ˆ‘”•‡†á ™Š‡”‡ƒ• ‹• –Š‡ •‡…‘•† ’‡”‹‘† ˆŽƒ– ‰‘Ž† ’Žƒ–‡Ž‡–• ‰”‘™ —’ ƒ– –Š‡ ’‡”‹’Š‡”› ‘ˆ •‘ˆ– ’ƒ”–‹…Ž‡ ƒ‰‰”‡‰ƒ–‡•ä Š‹• ’”‘…‡•• …ƒ• „‡ †‡•…”‹„‡† „› •–™ƒŽ† ”‹’‡•‹•‰ä ƒ”–‹…Ž‡ ƒ‰‰”‡‰ƒ–‡ †‡æ…‘•’‘•‹–‹‘• ’”‘…‡‡†• ‹• –Š‡ –Š‹”† ’‡”‹‘†ä
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•‹…”‘‰”ƒ’Š• Šƒ˜‡ ƒŽ”‡ƒ†› •Š‘™• –Šƒ– –Š‡ ”‡†—…–‹‘• ’”‘…‡•• –‘ ˆ‘”• ‰‘Ž† •ƒ•‘’ƒ”–‹…Ž‡• •–ƒ”–• ƒ– –Š‡ •—”ˆƒ…‡ ‘ˆ •‹š‡† ••ƒŽŽ —•‹Žƒ•‡ŽŽƒ” ˜‡•‹…Ž‡•
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ƒ˜‡”ƒ‰‹•‰ –‹•‡ ‹•–‡”˜ƒŽ• ‘ˆ –‡• •‹•—–‡•ä Š‡ ‰‘Ž† šæ”ƒ› •…ƒ––‡”‹•‰ …‘•–”ƒ•– ‘ˆ särw{x srst …•æt ‹• –Š”‡‡ ‘”†‡”• ‘ˆ •ƒ‰•‹–—†‡ Žƒ”‰‡” –Šƒ• –Šƒ– ‘ˆ –Š‡ ˜‡•‹…Ž‡• ƒ•† –Š‡”‡ˆ‘”‡ ™‡ ò•‡‡ó ‡š…Ž—•‹˜‡Ž› –Š‡ ‰‘Ž† ’ƒ”–‹…Ž‡•ä • ‘–Š‡” ™‘”†•á ™‡ òŽ‘‘•ó ‹•–‘ –Š‡ ˜‡•‹…Ž‡•ä –ƒ–‹•–‹…ƒŽŽ› •‹‰•‹ˆ‹…ƒ•– ‡••‡•„Ž‡ ƒ˜‡”ƒ‰‡• ‘ˆ –Š‡ •…ƒ––‡”‹•‰ ’ƒ––‡”• ™‡”‡ ’”‘˜‹†‡† „› ƒ• ‹””ƒ†‹ƒ–‡† ˜‘Ž—•‡ ‘ˆ sr Á ä šƒ•’Ž‡• ˆ‘” –Š‡ •…ƒ––‡”‹•‰ ’”‘ˆ‹Ž‡ ƒ– ƒ• ‡ƒ”Ž› •–ƒ‰‡ ƒ•† ƒ– –Š‡ ‡•† ‘ˆ –Š‡ ”‡ƒ…–‹‘• ƒ”‡ •Š‘™• ‹• ‹‰—”‡ wä ‘” ”‡ƒ…–‹‘• –‹•‡• ‘ˆ – ¶ xr •‹• –Š‡ …—”˜‡• …ƒ• „‡ ˆ‹––‡† „› •‹•’Ž‡ •’Š‡”‡• ™‹–Š ”ƒ†‹—• ‘ˆ xäw ¬ räv •• ƒ• •Š‘™• ‹• –Š‡ —’’‡” ‹••‡– ‘ˆ ‹‰—”‡ wä Š‡ •Šƒ’‡ ‘ˆ –Š‡ •…ƒ––‡”‹•‰ …—”˜‡• ˆ‘” ”‡ƒ…–‹‘• –‹•‡• Žƒ”‰‡” –Šƒ• xr •‹• …ƒ••‘– „‡ ‹•–‡”’”‡–‡† ‹• –‡”•• ‘ˆ •’Š‡”‹…ƒŽ ’ƒ”–‹…Ž‡•ä ‘” –Š‡‹” ‹•–‡”’”‡–ƒ–‹‘• ™‡ ˆ‹––‡† –Š‡ •…ƒ––‡”‹•‰ …—”˜‡• ™‹–Š –Š‡ •‘†‡Ž •…ƒ––‡”‹•‰ ˆ—•…–‹‘• ‘ˆ ƒ –Š‹• †‹•• ‹••–‡ƒ† ‘ˆ ƒ •ƒ•‘–”‹ƒ•‰Ž‡ „‡…ƒ—•‡ –Š‡ •…ƒ––‡”‹•‰ ˆ—•…–‹‘• ˆ‘” –Š‡ Žƒ––‡” ‹• •‘– ƒ˜ƒ‹Žƒ„Ž‡ ˆ‘” …—”˜‡ ˆ‹–•ätv Š‹• •‹•’Ž‹ˆ‹‡† •…ƒ––‡”‹•‰ •‘†‡Ž ™ƒ• ˆ‘—•† ƒ’’Ž‹…ƒ„Ž‡ ‘˜‡” ƒ ™‹†‡ “攃•‰‡ ˆ‘” ”‡ƒ…–‹‘• –‹•‡• Žƒ”‰‡” –Šƒ• xr •‹•ä • ‡šƒ•’Ž‡ ‘ˆ •‡ƒ•—”‡† ƒ•† ˆ‹––‡† …—”˜‡•á ”‡•—Ž–‹•‰ ‹• ƒ •‡ƒ• ’ƒ”–‹…Ž‡ –Š‹…••‡•• ‘ˆ yäs ¬ räs •• ƒ•† ƒ •‡ƒ• †‹ƒ•‡–‡” ‘ˆ tu ¬ s •• …ƒ• „‡ •‡‡• ‹• ‹‰—”‡ w „Žƒ…• ƒ•† „Ž—‡ Ž‹•‡á ”‡•’‡…–‹˜‡Ž› ä Š‡ ”‡ƒ…–‹‘• –‹•‡ ™ƒ• – ± tuw •‹•ä Š‡ ‹••‡– ˜‹•—ƒŽ‹œ‡† –Š‡ ‹†‡ƒŽ •ƒ•‘–”‹ƒ•‰Ž‡ ƒ•† ƒ †‹•• ™‹–Š –Š‡ •ƒ•‡ ’Žƒ–‡Ž‡– –Š‹…••‡•• ƒ•† –Š‡ •ƒ•‡ ”ƒ†‹—• ‘ˆ ‰›”ƒ–‹‘• ƒ• —•‡† ˆ‘” ˆ‹––‹•‰ä – ‹• ‘„˜‹‘—• –Šƒ– –Š‹• †‹•• •‘†‡Ž ‹• ‘˜‡”•‹•’Ž‹ˆ‹‡† ƒ– Žƒ”‰‡ •…ƒ––‡”‹•‰ ˜‡…–‘”• „—– –Š‹• ‹• •‘– …”‹–‹…ƒŽ ˆ‘” ‘—” ‹•–‡”’”‡–ƒ–‹‘•ä ‡ †‹† •‘– ‹•…Ž—†‡ ƒ• ƒ•ƒŽ›•‹• ‘ˆ ’‘Ž›†‹•’‡”•‹–› –‘ ƒ˜‘‹† ƒ•„‹‰—‘—• ”‡•—Ž–• †—‡ –‘ –Š‡ †ƒ•‰‡” ‘ˆ ‘˜‡”ˆ‹––‹•‰ä • ‹•…”‡ƒ•‡ ‘ˆ –Š‡ •…ƒ––‡”‹•‰ ‹•–‡••‹–›á ™Š‡”‡ –Š‡ †ƒ–ƒ ’‘‹•–• Ž‹‡ ƒ„‘˜‡ –Š‡ •‘†‡Ž …—”˜‡•á ‹• ˜‹•‹„Ž‡ ƒ– “昃Ž—‡• Ž‘™‡” –Šƒ– rärw ••æsä Š‹• …‘””‡•’‘•†• –‘ †‹•–ƒ•…‡• Žƒ”‰‡” –Šƒ• N rärw •• ± xt •• •‡‡ ƒ””‘™• ‹• ‹‰—”‡ w ƒ•† ‹•†‹…ƒ–‡• –Šƒ– ‡ˆˆ‡…–• ‘ˆ ƒ‰‰”‡‰ƒ–‹‘• ƒ”‡ •‘– ‹•–‡”ˆ‡”‹•‰ ™‹–Š –Š‡ ’ƒ”–‹…Ž‡ •…ƒ––‡”‹•‰ä —”’”‹•‹•‰Ž› •‘ •–”—…–—”‡ ˆƒ…–‘” •‡‡†• –‘ „‡ –ƒ•‡• ‹•–‘ ƒ……‘—•–ä Šƒ– •‡ƒ•• –Šƒ– –Š‡ ‹•†‹˜‹†—ƒŽ ’ƒ”–‹…Ž‡• ƒ”‡ ƒŽ”‡ƒ†› •‹‰•‹ˆ‹…ƒ•–Ž› •‡’ƒ”ƒ–‡† ˆ”‘• ‡ƒ…Š ‘–Š‡” ™‹–Š‹• Ž‘‘•‡Ž› ’ƒ…•‡†á •‘ˆ– ƒ‰‰”‡‰ƒ–‡ •–”—…–—”‡• •Š‘™• ‹• ‹‰—”‡ srä • …‘•–”ƒ•–á ˆ‘” †‡••‡Ž› ’ƒ…•‡† ƒ‰‰”‡‰ƒ–‡• ™‡ •—•– ‡š’‡…– ƒ •—…Š •–”‘•‰‡” ‹•…”‡ƒ•‡ ‘ˆ –Š‡ •…ƒ––‡”‹•‰ ‹•–‡••‹–› ™‹–Š ƒ• ‡ƒ”Ž› ‘••‡– –Šƒ– ‹•–‡”ˆ‡”‡• •–”‘•‰Ž› ™‹–Š –Š‡ ’ƒ”–‹…Ž‡ ˆ‘”• ˆƒ…–‘”ä
ACS Paragon Plus Environment
,QWHQVLW\ >P @
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Langmuir
,QWHQVLW\ P
Page 11 of 22
T QP
T >QP @ ‹‰—”‡ wä
‹•–‡••‹–› ƒ• ƒ ˆ—•…–‹‘• ‘ˆ –Š‡ •…ƒ––‡”‹•‰ ˜‡…–‘” ƒ•† ƒ …—”˜‡ ˆ‹– ‘ˆ ƒ •ƒ•‘æ
†‹•• ‰‘Ž† ’ƒ”–‹…Ž‡ ™‹–Š ƒ •‡ƒ• Š‡‹‰Š– ‘ˆ yäs ¬ räs •• ƒ•† ƒ †‹ƒ•‡–‡” ‘ˆ tu ¬ s ••ä Š‡ ”‡ƒ…–‹‘• –‹•‡ ™ƒ• – ± tuw •‹•ä Š‡ Ž‘™‡” ‹••‡– •Š‘™• ƒ •ƒ•‘–”‹ƒ•‰Ž‡ ƒ•† ƒ •ƒ•‘憋•• ™‹–Š –Š‡ •ƒ•‡ –Š‹…••‡•• ƒ•† –Š‡ •ƒ•‡ ”ƒ†‹—• ‘ˆ ‰›”ƒ–‹‘•ä Š‡ —’’‡” ‹••‡– •Š‘™• –Š‡ •…ƒ––‡”‹•‰ ‘ˆ ƒ •’Š‡”‡ ™‹–Š ƒ ”ƒ†‹—• ‘ˆ
± xäw ¬ räv •• •‡ƒ•—”‡† ƒ– – ± ux •‹•ä ””‘™•
‹•†‹…ƒ–‡ –Š‡ ‘••‡– ‘ˆ ‹•…”‡ƒ•‡ ‘ˆ –Š‡ •…ƒ––‡”‹•‰ ‹•–‡••‹–› †—‡ –‘ ƒ‰‰”‡‰ƒ–‹‘•ä
• ‘˜‡”˜‹‡™ ‘ˆ –Š‡ ’ƒ”–‹…Ž‡ •‹œ‡ ’ƒ”ƒ•‡–‡”• ƒ• †‡”‹˜‡† ˆ”‘• –Š‡ •‘†‡Ž ˆ‹–• ‹• ‰‹˜‡• ‹• ‹‰—”‡ xä – …ƒ• „‡ •‡‡• –Š‡”‡ –Šƒ– –Š‡ •’Š‡”‹…ƒŽ ’ƒ”–‹…Ž‡• †‹•’Žƒ› •‡ƒ• †‹ƒ•‡–‡”• ‘ˆ ƒ„‘—– su •• ™‹–Š ”‡Žƒ–‹˜‡Ž› Žƒ”‰‡ —•…‡”–ƒ‹•–‹‡• ‹• ’‡”‹‘† sä
‡š– –Š‡ –Š‹…••‡••‡•
‹•…”‡ƒ•‡ ˆ”‘• wäs •• ƒ– – ± x{ •‹• –‘ yäw •• ƒ– – ± szu •‹• ‹• ’‡”‹‘† tä Š‡”‡‹• –Š‡ †‹ƒ•‡–‡”• ‹•…”‡ƒ•‡ ˆ”‘• sxä{ •• –‘ tuär ••ä
– Žƒ–‡” –‹•‡•á ‹• ’‡”‹‘† uá –Š‡ •‹œ‡
’ƒ”ƒ•‡–‡”• ƒ”‡ …‘••–ƒ•– ƒ•† –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡• ƒ”‡ ˆ—ŽŽæ‰”‘™•ä ‡ “—ƒ•–‹ˆ‹‡† –Š‡ ˜‘Ž—•‡ ‘ˆ –Š‡ ’ƒ”–‹…Ž‡• ƒ•
± v u N ”ƒ†‹‹u ‹• ’‡”‹‘† s ƒ•† ƒ•
± –Š‹…••‡•• - N †‹ƒ•‡–‡”t ‹• ’‡”‹‘† t ƒ•† uä Š‡ ˜‘Ž—•‡• ƒ”‡ …‘••–ƒ•– ‹• ’‡”‹‘† sá ‹•…”‡ƒ•‡ Ž‹•‡ƒ”Ž› ‹• ’‡”‹‘† t ƒ•† ƒ”‡ ƒ‰ƒ‹• …‘••–ƒ•– ‹• ’‡”‹‘† u ƒ• …ƒ• „‡ •‡‡• ‹• ‹‰—”‡ yä
‡ “—ƒ•–‹ˆ‹‡† –Š‹• ‘„•‡”˜ƒ–‹‘• „› 8:P; L 85 8:P; L > E IÏ P 8:P; L 86
ˆ‘” P Q P5áÏ ˆ‘” P5áÏ O P O P6áÏ ˆ‘” P R P6áÏ
ACS Paragon Plus Environment
Langmuir
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Š‡ • ‹• –Š‡ ‰”‘™–Š ”ƒ–‡ ‘ˆ –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡ ˜‘Ž—•‡•á –Š‡ –”‹ƒ•‰Ž‡• •–ƒ”– –‘ ‰”‘™ ƒ•†
t
s
‹• –Š‡ ’ƒ”–‹…Ž‡ï• ˜‘Ž—•‡ ™Š‡•
‹• –Š‡ ˆ‹•ƒŽ ˜‘Ž—•‡ ‘ˆ –Š‡ –”‹ƒ•‰Ž‡•ä Š‡ ‹•‹–‹ƒŽ –‹•‡ ˆ‘”
–Š‡ ˆ‹”•– ‘„•‡”˜ƒ–‹‘• ‘ˆ –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡• ‹• P5áÏ L :85 F >; IÏ ƒ•† –Š‡› •–‘’’‡† ‰”‘™‹•‰ ƒ– P6áÏ L :86 F >; IÏ ä Š‡ …—”˜‡ ˆ‹– —•‹•‰ ‡“ä s ”‡•—Ž–• ‹• ƒ•†
t
s
± ssxu ¬ us ••u
± t{xr ¬ us ••uä •‹•‰ –Š‹• ƒ’’”‘ƒ…Š –Š‡ ’‡”‹‘† s ‡•†• ƒ– –sá ± xz ¬ u •‹• ƒ•†
’‡”‹‘† u •–ƒ”–• ƒ– –tá ± szr ¬ t •‹•ä Š‡ ˜‘Ž—•‡ ‰”‘™–Š ”ƒ–‡ ‘ˆ –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡• ‹• • ± sxäs ¬ räu ••u •‹•æs ‹• ’‡”‹‘† tä ‡š–á ‹– ‹• ‘ˆ ‹•–‡”‡•– Š‘™ –Š‡ –Š‹…••‡•• ƒ•† –Š‡ †‹ƒ•‡–‡” ‘ˆ –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡• …‘•–”‹„—–‡ –‘ –Š‡ ˜‘Ž—•‡ ‰”‘™–Šä
Š‡ ‰”‘™–Š ‘ˆ –Š‡ –Š‹…••‡•• ‹• ’‡”‹‘† t ‹• Ž‹•‡ƒ” ™Š‹Ž‡ –Š‡
‹•…”‡ƒ•‡ ‘ˆ –Š‡ †‹ƒ•‡–‡” ‹• •‘•Ž‹•‡ƒ” ƒ• …ƒ• „‡ •‡‡• ‹• ‹‰—”‡ xä ‹•‹Žƒ” –‘ ‡“ä s ™‡ “—ƒ•–‹ˆ‹‡† –Š‡ •ƒ•‘æ’Žƒ–‡ –Š‹…••‡•• ƒ• D :P; L D5 D:P; L >Û E IÛ P D:P; L D6
ˆ‘” P Q P5áÛ ˆ‘” P5áÛ O P O P6áÛ ˆ‘” P R P6áÛ
Š‡ ”‡•—Ž–ƒ•– ˆ‹– ƒ• •Š‘™• ‹• ‹‰—”‡ x „Žƒ…• •‘Ž‹† Ž‹•‡ ”‡•—Ž–• ‹• ƒ• ‹•‹–‹ƒŽ –Š‹…••‡•• ‘ˆ Šs ± wäs ¬ räu •• ƒ•† ƒ ˆ‹•ƒŽ –Š‹…••‡•• ‘ˆ Št ± yäs ¬ räs ••ä
Š‡ ’‡”‹‘† s ‡•†• ƒ–
–sአ± yz ¬ su •‹• ƒ•† ’‡”‹‘† t ƒ– –tአ± szr ¬ t •‹•ä Š‡ ‰”‘™–Š ”ƒ–‡ ‘ˆ –Š‡ –Š‹…••‡•• ‘ˆ –Š‡ –”‹ƒ•‰Ž‡• ‹• •Š ± rärtr ¬ rärrs •• •‹•æs ‹• ’‡”‹‘† tä ‹•…‡ ˜‘Ž—•‡ ƒ•† –Š‹…••‡•• ‘ˆ –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡• ‰”‘™ Ž‹•‡ƒ” ‹• ’‡”‹‘† t ‹– ‹• •–”ƒ‹‰Š–ˆ‘”™ƒ”† –Šƒ– –Š‡ †‹ƒ•‡–‡”• ‰”‘™ ’”‘’‘”–‹‘•ƒŽ –‘ –Š‡ •“—ƒ”‡ ”‘‘– ‘ˆ –‹•‡ä Š‡”‡ˆ‘”‡á ™‡ “—ƒ•–‹ˆ‹‡† –Š‡ †‹ƒ•‡–‡” ƒ• @ :P; L @5 @:P; L @5 E G ¥P F P5á× @:P; L @6
ˆ‘” P Q P5á× ˆ‘” P5á× O P O P6á× ˆ‘” P R P6á×
Š‡ ”‡•—Ž– ‘ˆ —•‹•‰ ‡“ä u ˆ‘” ‹•–‡”’”‡–ƒ–‹‘• ‘ˆ –Š‡ †‹ƒ•‡–‡” ‹• •Š‘™• ‹• ‹‰—”‡ x ”‡† •‘Ž‹† Ž‹•‡ ä
•‹•‰ –Š‹• ƒ’’”‘ƒ…Šá –Š‡ ‹•‹–‹ƒŽ –‹•‡ ™Š‡• –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡• ƒ”‡ ˆ‹”•–
‘„•‡”˜‡† ‹• –sᆠ± xz ¬ tä
Š‡ ‡•† ‘ˆ –Š‡ ‰”‘™–Š ‘ˆ –Š‡ †‹ƒ•‡–‡” ‹• P6á× L P5á× E
:@6 F @5 ;6 G 6 ‹• ± szr ¬ w •‹•ä Š‡ ‰”‘™–Š …‘••–ƒ•– ‹• • ± räxws ¬ rärt{ •• •s tä ACS Paragon Plus Environment
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‘™ ™‡ …ƒ• …‘•’ƒ”‡ –Š‡ ‰”‘™–Š ”ƒ–‡ ‘ˆ –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡•ï –Š‹…••‡••á D6 :P; L IÛ á ™‹–Š –Š‡ ‰”‘™–Š ”ƒ–‡ ‘ˆ –Š‡‹” †‹ƒ•‡–‡”á @6 :P; L G kt ¥P F P5á× oá ˆ‘” –‹•‡• „‡–™‡‡• –sᆠƒ•† –tá†ä ‹‰—”‡ y †‡•‘••–”ƒ–‡ –Šƒ– –Š‡ ‰”‘™–Š ”ƒ–‡ ‘ˆ –Š‡ †‹ƒ•‡–‡” ‹• ƒ– ƒ•› –‹•‡ Žƒ”‰‡” –Šƒ• –Š‡ ‰”‘™–Š ”ƒ–‡ ‘ˆ –Š‡ Š‡‹‰Š– ”‡† •‘Ž‹† ƒ•† „Žƒ…• †ƒ•Š‡† Ž‹•‡á ”‡•’‡…–‹˜‡Ž› ä Š‡ ”ƒ–‹‘ ‘ˆ –Š‡ ‰”‘™–Š ”ƒ–‡•á @6 :P; D6 :P; L G kt IÛ ¥P F P5á× oá ƒŽŽ‘™• ƒ †‹”‡…– …‘•’ƒ”‹•‘• „Ž—‡ †‘––‡† Ž‹•‡ ‹• ‹‰—”‡ y ä Š—•á –Š‡ ‰”‘™–Š ”ƒ–‡ ‘ˆ –Š‡ †‹ƒ•‡–‡” ‹• sx –‹•‡• Žƒ”‰‡” –Šƒ• –Šƒ– ‘ˆ –Š‡
7KLFNQHVV >QP@
Š‡‹‰Š– ƒ– – ± x{ •‹• ƒ•† †‡…”‡ƒ•‡• –‘ säw –‹•‡• ƒ– – ± sy{ •‹• ‹•†‹…ƒ–‡† „› ƒ””‘™• ä
'LDPHWHU >QP@
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
Langmuir
7LPH >PLQ@ ‹‰—”‡ xä ƒ”–‹…Ž‡ •‹œ‡ ’ƒ”ƒ•‡–‡”• ƒ• ƒ ˆ—•…–‹‘• ‘ˆ –Š‡ ”‡ƒ…–‹‘• –‹•‡ä ‹˜‡• ƒ”‡ –Š‡ •‡ƒ• †‹ƒ•‡–‡” ‘ˆ •’Š‡”‹…ƒŽ ’ƒ”–‹…Ž‡• „Ž—‡ …”‘••‡• ƒ– – ¶ xr •‹• ’‡”‹‘† s ä – Žƒ–‡” –‹•‡• –Š‹…••‡••‡• ƒ•† †‹ƒ•‡–‡”• ‘ˆ ’Žƒ–‡æŽ‹•‡ ’ƒ”–‹…Ž‡• ƒ”‡ ’Ž‘––‡† „Žƒ…• …‹”…Ž‡• ƒ•† ”‡† •“—ƒ”‡•á ”‡•’‡…–‹˜‡Ž› †—”‹•‰ •ƒ•‘–”‹ƒ•‰Ž‡ ‰”‘™‹•‰ ƒ– xr •‹• ´ – ´ szr •‹• ’‡”‹‘† t ƒ•† ƒ• ˆ—ŽŽæ‰”‘™• •ƒ•‘–”‹ƒ•‰Ž‡• – µ szr •‹• ’‡”‹‘† u ä
ACS Paragon Plus Environment
5DWLR RI JURZWK UDWHV
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*URZWK UDWHV >QP PLQ@
Langmuir
7LPH >PLQ@ ‹‰—”‡ yä ”‘™–Š ”ƒ–‡• ‘ˆ –Š‡ –Š‹…••‡•• ƒ•† †‹ƒ•‡–‡” ‹• ’‡”‹‘† t „Žƒ…• †ƒ•Š‡† ƒ•† ”‡† •‘Ž‹† Ž‹•‡á ”‡•’‡…–‹˜‡Ž› ä Š‡ ‰”‘™–Š ”ƒ–‡ ‘ˆ –Š‡ –Š‹…••‡••‡• ‹• D6 :P; L IÛ ± rärtr ¬ rärrs •• •‹•æsä Š‡ ‰”‘™–Š ”ƒ–‡ ‘ˆ –Š‡ †‹ƒ•‡–‡”• ‹• @6 :P; L G kt ¥P F P5á× oá ™‹–Š • ± räxws ¬ rärt{ •• •s
t
ƒ•† –sᆠ± xz ¬ tä
Š‡ ”ƒ–‹‘ ‘ˆ –Š‡ ‰”‘™–Š ”ƒ–‡• ‹• @6 :P; D6 :P; L G
kt IÛ ¥P F P5á× o „Ž—‡ †‘––‡† Ž‹•‡ ä Š‹• ”ƒ–‹‘ †‡…”‡ƒ•‡• ˆ”‘• sx ƒ– – ± x{ •‹• –‘ säw ƒ– – ± sy{ •‹• ‹•†‹…ƒ–‡† „› ƒ””‘™• ä
Š‡ ˜‘Ž—•‡ ˆ”ƒ…–‹‘•á Ö – ‘ˆ –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡• ƒ• ƒ ˆ—•…–‹‘• ‘ˆ –‹•‡ ™‡”‡ †‡–‡”•‹•‡† ƒ• †‡•…”‹„‡† ”‡…‡•–Ž›átv ƒ•† †‹•’Žƒ›‡† ‹• ‹‰—”‡ zä ‹•…‡ –Š‡ ˜‘Ž—•‡ ‹•…”‡ƒ•‡• Ž‹•‡ƒ”Ž› ‹• ’Šƒ•‡ t ™‡ “—ƒ•–‹ˆ‹‡† –Š‡ –‹•‡ †‡’‡•†‡•…‡ ‘ˆ –Š‡ ˜‘Ž—•‡ ˆ”ƒ…–‹‘• ƒ•ƒŽ‘‰‘—•Ž› –‘ ‡“ä s ä Š‡ ”‡•—Ž–• ƒ”‡ ‰‹˜‡• ‹• ‹‰—”‡ zä ‘” –Š‡ ˜‘Ž—•‡ ˆ”ƒ…–‹‘• ™‡ ˆ‘—•† –Šƒ– ’‡”‹‘† s ‡•†• ƒ– –sáÖ± xu ¬ t •‹• ™Š‡”‡ –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡ ˆ”ƒ…–‹‘• ‹• Ö –sáÖ ± rä
Š‡ ˜‘Ž—•‡ ˆ”ƒ…–‹‘• ‘ˆ –”‹ƒ•‰Ž‡• ‹•…”‡ƒ•‡• ™‹–Š ƒ
•Ž‘’‡ ‘ˆ •Ö ± sär{ ¬ rärv - sræy •‹•æs „‡–™‡‡• –sáÖ ƒ•† –táÖä –táÖ ± syx ¬ u •‹• ™Š‡”‡ Ö –táÖ ± sätv ¬ rärv - sræwä
‡”‹‘† u „‡‰‹•• ƒ–
—Ž–‹’Ž‹…ƒ–‹‘• ‘ˆ –Š‹• ˆ‹•ƒŽ ˜‘Ž—•‡
ˆ”ƒ…–‹‘• ™‹–Š –Š‡ „—Ž• †‡••‹–› ‘ˆ ‰‘Ž† ‰‹˜‡• ƒ •ƒ•‘–”‹ƒ•‰Ž‡ ‰‘Ž† …‘•…‡•–”ƒ–‹‘• ‘ˆ rätvw ‰ æsä
Š‹• ‹• ƒ„‘—– sy¨ Ž‡•• –Šƒ• –Š‡ –‘–ƒŽ …‘•…‡•–”ƒ–‹‘• ‘ˆ rät{w ‰
æs
‰‘Ž† ‹• ˆ‘”• ‘ˆ ‰‘Ž†
•ƒŽ– —•‡† ˆ‘” –Š‡ •›•–Š‡•‹•ä Š‡”‡ˆ‘”‡á ™‡ …ƒ• ‡•–‹•ƒ–‡ –Šƒ– ƒ„‘—– zu¨ ‘ˆ –Š‡ ‰‘Ž† ‹• ˆ‹•ƒŽŽ› ˆ‘—•† ‹• –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡•ä
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‹‰—”‡ zä Š‡ ˜‘Ž—•‡ ˆ”ƒ…–‹‘• ‘ˆ –Š‡ –”‹ƒ•‰Ž‡• ƒ• ƒ ˆ—•…–‹‘• ‘ˆ ”‡ƒ…–‹‘• –‹•‡ä ‘Ž‹† Ž‹•‡• ƒ”‡ –Š‡ …‘””‡•’‘•†‹•‰ …—”˜‡ ˆ‹–•ä
9ROXPH >QP @
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0RODU PDVV >J PRO@
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
Langmuir
7LPH >PLQ@ ‹‰—”‡ {ä
‡ƒ• ˜‘Ž—•‡ ‘ˆ –Š‡ ’ƒ”–‹…Ž‡• ƒ• ƒ ˆ—•…–‹‘• ‘ˆ –‹•‡ ƒ•† …‘””‡•’‘•†‹•‰ …—”˜‡ ˆ‹–
•“—ƒ”‡• ƒ•† •‘Ž‹† Ž‹•‡á ”‡•’‡…–‹˜‡Ž› ä Š‡ ”‹‰Š– ƒš‹• ‹• –Š‡ •‘Žƒ” •ƒ•• ‘ˆ –Š‡ –”‹ƒ•‰Ž‡• ’”‡•—•‹•‰ –Š‡ •ƒ•‡ †‡••‹–› ƒ• ‰‘Ž† ‹• „—Ž• •–ƒ–‡ ‘ˆ s{äu ‰ …•uä
‹‰—”‡ { •Š‘™• –Š‡ –‹•‡ †‡’‡•†‡•– ‹•…”‡ƒ•‡ ‘ˆ –Š‡ ˜‘Ž—•‡ ƒ•† •‘Žƒ” •ƒ•• ‘ˆ –Š‡ –”‹ƒ•‰Ž‡•ä Š‡ Ž‹•‡ƒ” ‹•…”‡ƒ•‡ ‹• –Š‡ •‡ƒ• ’ƒ”–‹…Ž‡ ˜‘Ž—•‡ ™‹–Š –‹•‡ …ƒ• „‡ †‡•…”‹„‡† „› ƒ †‹ˆˆ—•‹‘•æŽ‹•‹–‡†
•–™ƒŽ† ”‹’‡•‹•‰äur
—‡ –‘ –Š‡ †‡…”‡ƒ•‡ ‘ˆ •—’‡”•ƒ–—”ƒ–‹‘• ‹• ƒ
…Ž‘•‡† •›•–‡• ••ƒŽŽ‡” …”›•–ƒŽ• ™‹–Š ƒ ”ƒ†‹—• ” „‡Ž‘™ ƒ …”‹–‹…ƒŽ ˜ƒŽ—‡ ”
ACS Paragon Plus Environment
•—•– †‹••‘Ž˜‡
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™Š‡”‡ƒ• Žƒ”‰‡” …”›•–ƒŽ• ™‹–Š ”µ” •—•– ‰”‘™äus
Š‹• ’”‘…‡•• ‹• –Š‡”•‘†›•ƒ•‹…ƒŽŽ›
’”‡ˆ‡””‡†á ƒ•† …ƒ• „‡ ‡š’Žƒ‹•‡† ˆ‘” Žƒ”‰‡ ’ƒ”–‹…Ž‡• „› ƒ •ƒ–Š‡•ƒ–‹…ƒŽ ƒ’’”‘ƒ…Šá †‡˜‡Ž‘’‡† „›
‹ˆ•Š‹–œá
Ž›‘œ‘˜á ƒ•†
ƒ‰•‡”äutáuu
• •‹–— –‹•‡ ”‡•‘Ž˜‡†
•‡ƒ•—”‡•‡•–• Šƒ˜‡ •Š‘™• –Šƒ– –Š‡ ‰”‘™–Š ‘ˆ ”Š‘†‹—• ƒ•† ’ƒŽŽƒ†‹—• •ƒ•‘’ƒ”–‹…Ž‡• ‹• ƒ• ƒ“—‡‘—• ‡–Šƒ•‘Ž •‘Ž—–‹‘• ‹• ’”‡•‡•…‡ ‘ˆ
’”‘…‡‡†‡† ˜‹ƒ ƒ•
•–™ƒŽ† ”‹’‡•‹•‰æ
„ƒ•‡† ‰”‘™–Š •‡…Šƒ•‹••áur ‹• …‘•–”ƒ•– –‘ ‰‘Ž† •ƒ•‘’ƒ”–‹…Ž‡•äuv
uäwä
”‘™–Š •‡…Šƒ•‹••
ƒ•‡† ‘• –Š‡ ”‡•—Ž–• •Š‘™• Š‡”‡ –Š‡ –‹•‡ †‡’‡•†‡•– ‰‘Ž† •ƒ•‘–”‹ƒ•‰Ž‡ ˆ‘”•ƒ–‹‘• ’”‘…‡•• …ƒ• „‡ †‹˜‹†‡† ‹•–‘ †‹ˆˆ‡”‡•– ’‡”‹‘†•ã
æ
‡”‹‘† ã ræxr •‹•
• –Š‡ ˆ‹”•– Š‘—” –Š‡ ”ƒ†‹—• ‘ˆ –Š‡ ‰‘Ž† •ƒ•‘’ƒ”–‹…Ž‡• †‡–‡”•‹•‡† „›
‹• “—‹–‡
…‘••–ƒ•– ƒ– xäw ¬ räv ••á ‹•†‹…ƒ–‹•‰ –Šƒ– •’Š‡”‹…ƒŽ ’ƒ”–‹…Ž‡• ƒ”‡ ˆ‘”•‡†ä
Š‡•‡
•ƒ•‘’ƒ”–‹…Ž‡• ƒ”‡ ˆ‘”•‡† ƒ– –Š‡ „‹Žƒ›‡” ‘ˆ –Š‡ •‹š‡† ˜‡•‹…Ž‡• „› ƒ ò…Žƒ••‹…ƒŽó •—…Ž‡ƒ–‹‘• ’”‘…‡••ä ••‹†‡ ‘ˆ –Š‡ •—Ž–‹˜‡•‹…—Žƒ” ˜‡•‹…Ž‡• …‘•’ƒ”‡ ‹‰—”‡ s á ™Š‡”‡ –Š‡ •—•„‡” ‘ˆ Œ—•…–‹‘• ’‘‹•–• „‡–™‡‡• –Š‡
’Š‘•’Š‘Ž‹’‹† „‹Žƒ›‡”• ‹• •—…Š Š‹‰Š‡” ‹• •‹•‹Žƒ”‹–› –‘
–—„—Žƒ” •‡–™‘”••át{ –Š‡ Ž‘…ƒŽ …‘•…‡•–”ƒ–‹‘• ‘ˆ ‹•†‹˜‹†—ƒŽ ˆ‘”•‡† ‰‘Ž† •ƒ•‘’ƒ”–‹…Ž‡• ‹• ƒŽ•‘ ‹•…”‡ƒ•‡†ä
•‹…”‘‰”ƒ’Š•á ’‡”ˆ‘”•‡† ƒˆ–‡” xr •‹•—–‡•á ‹ŽŽ—•–”ƒ–‡ –Šƒ– –Š‡•‡
•ƒ•‘…”›•–ƒŽŽ‹–‡• „—‹Ž† —’ •‘ˆ– ’ƒ”–‹…Ž‡ ƒ‰‰”‡‰ƒ–‡• ‘ˆ ƒ„‘—– syr •• ‹• •‹œ‡ä – …ƒ• „‡ ƒ••—•‡† –Šƒ–
’Žƒ›• ƒ• ‹•’‘”–ƒ•– ”‘Ž‡ ‹• –Š‡ ƒ‰‰”‡‰ƒ–‹‘• ’”‘…‡••á ‹• ƒ•ƒŽ‘‰› –‘ –Š‡
”‡•—Ž–• •Š‘™• „› —Œƒ• ‡– ƒŽätx ’—„Ž‹•Š‡† ”‡•—Ž–• ™‹–Š
æ
•Š‘™• •‹•‹Žƒ” ‡ˆˆ‡…–•txá ™Š‹…Š ‡š’Žƒ‹•• ’”‡˜‹‘—•Ž›
’Š‘•’Š‘Ž‹’‘• ˜‡•‹…Ž‡•ätr
‡”‹‘† ã xr æszr •‹• •‡ƒ•—”‡•‡•–• •Š‘™ –Šƒ– ƒˆ–‡” ‘•‡ Š‘—” ˆŽƒ– •ƒ•‘…”›•–ƒŽ• ƒ”‡ ˆ‘”•‡†ä Š‡ ‹•‹–‹ƒŽ
’Žƒ–‡Ž‡– –Š‹…••‡•• ‘ˆ wäs ¬ räu •• ‹• ‹•…”‡ƒ•‡† ‘•Ž› •ƒ”‰‹•ƒŽ —’ –‘ yäs ¬ räs ••á ™Š‡”‡ƒ• –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡ †‹ƒ•‡–‡” ƒ• ™‡ŽŽ ƒ• –Š‡ ˜‘Ž—•‡ ƒ•† •‘Žƒ” •ƒ••
‹‰—”‡ { ƒ”‡
‹•…”‡ƒ•‡† Ž‹•‡ƒ”Ž›ä Š‡ ‰”‘™–Š ”ƒ–‡ ‹• Žƒ–‡”ƒŽ †‹”‡…–‹‘• ‹• sx –‹•‡• Žƒ”‰‡” –Šƒ• ‹• ˜‡”–‹…ƒŽ †‹”‡…–‹‘•ä Š‹• ’”‘…‡•• …ƒ• „‡ ™‡ŽŽ †‡•…”‹„‡† „› ƒ• •–™ƒŽ† ”‹’‡•‹•‰æ„ƒ•‡† ‰”‘™–Š ‘ˆ ‰‘Ž† •ƒ•‘–”‹ƒ•‰Ž‡•ä
‡”‡„› –Š‡ ’”‡Ž‹•‹•ƒ”› ˆ‘”•‡† ••ƒŽŽ •ƒ•‘…”›•–ƒŽ• ™‹–Š ”´”
†‹•ƒ’’‡ƒ” ™Š‡”‡ƒ• –Š‡ ˆŽƒ– •ƒ•‘’Žƒ–‡Ž‡–• ‹• –Š‡ ’‡”‹’Š‡”› ‘ˆ –Š‡ ƒ‰‰”‡‰ƒ–‡• ‰”‘™ —’ –‘ …‘”ƒŽæŽ‹•‡ •–”—…–—”‡•ä
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æ
‡”‹‘†
ã szr twr •‹•
ˆ–‡” szr •‹•—–‡• –Š‡ ‰”‘™‹•‰ ’”‘…‡•• ‹• Ž‡˜‡Ž‡† ‘ˆˆ ”‡•—Ž–‹•‰ ‹• …‘••–ƒ•– •ƒ•‘–”‹ƒ•‰Ž‡ †‹ƒ•‡–‡”á ˜‘Ž—•‡ ƒ•† •‘Žƒ” •ƒ••ä
Š‡
•‹…”‘‰”ƒ’Š• •Š‘™ –Šƒ– –Š‡ ’ƒ”–‹…Ž‡
ƒ‰‰”‡‰ƒ–‡• †‡…‘•’‘•‡ ‹•–‘ •ƒ•‘–”‹ƒ•‰Ž‡• ƒ•† •’Š‡”‹…ƒŽ ’ƒ”–‹…Ž‡•ä
Š‡ ’”‘’‘•‡† •‡…Šƒ•‹••• ˆ‘” –Š‡ ˆ‘”•ƒ–‹‘• ‘ˆ ‡•‡”‰‡–‹…ƒŽŽ› —•ˆƒ˜‘”ƒ„Ž‡ ƒ•‹•‘–”‘’‹… •ƒ•‘–”‹ƒ•‰Ž‡• ˆƒŽŽ ‹•–‘ –™‘ …ƒ–‡‰‘”‹‡• æ
„› ƒ††‹•‰ •›••‡–”› „”‡ƒ•‹•‰ …‘•’‘—•†• ƒ†•‘”„‹•‰ –‘ •’‡…‹ˆ‹… …”›•–ƒŽ ˆƒ…‡•
æ
„› —•‹•‰ –‡•’Žƒ–‡ ’Šƒ•‡• ƒ• •’ƒ…‡æ…‘•ˆ‹•‹•‰ •–”—…–—”‡•ä
• ‘—” …ƒ•‡ „‘–Š •‡…Šƒ•‹••• ƒ”‡ ‘ˆ ”‡Ž‡˜ƒ•…‡á –Š‹• •‡ƒ••á –Š‡ –‡•’Žƒ–‡ ‡ˆˆ‡…– ‘ˆ –Š‡ ˜‡•‹…Ž‡• ƒ•† –Š‡ ’”‡ˆ‡”‡•–‹ƒŽ ƒ†•‘”’–‹‘• ‘ˆ …ƒ’’‹•‰ ƒ‰‡•–•á ‹ä‡äá —” ”‡…‡•–Ž› ’—„Ž‹•Š‡†
ƒ•† ƒŽ Š ‹• ƒ”„ä
‹•˜‡•–‹‰ƒ–‹‘•• Šƒ˜‡ •Š‘™• –Šƒ– –Š‡ •ƒ•‘–”‹ƒ•‰Ž‡• ‡šŠ‹„‹–
˜‡”› Žƒ”‰‡ sss „‘––‘• ƒ•† –‘’ ˆƒ…‡• ƒ•† –™‹• ’Žƒ•‡• ‘”‹‡•–‡† ’ƒ”ƒŽŽ‡Ž –‘ –Š‡ •—„•–”ƒ–‡ ’Žƒ•‡ ™‹–Š ƒŽ–‡”•ƒ–‹•‰ …‘•…ƒ˜‡ ƒ•† …‘•˜‡š •‹†‡ ˆƒ…‡•äy Š‡”‡ˆ‘”‡á –Š‡ ‰”‘™–Š ‹• Žƒ–‡”ƒŽ †‹”‡…–‹‘• ‹• ’”‡ˆ‡””‡† ƒ– –Š‡ …‘•…ƒ˜‡ •‹†‡ ˆƒ…‡•á ƒ……‘”†‹•‰ –‘ –Š‡ •‘†‡Ž ’”‘’‘•‡† „› ‘ˆ–‘• ƒ•† ‹‰•—•†äuw
ƒ•† ƒŽ Š ‹• ƒ”„ …ƒ• „‹•† •‡Ž‡…–‹˜‡Ž› –‘ sss ˆƒ…‡–• ‘ˆ –Š‡
’Žƒ–‡Ž‡–• ƒ•† …ƒ• –Š‡”‡„› ”‡†—…‡ –Š‡ ‰”‘™–Š ”ƒ–‡ ‹• ˜‡”–‹…ƒŽ †‹”‡…–‹‘•äux ‘•ˆ‹•‡•‡•– ‡ˆˆ‡…–• ‹• –Š‡ …‘”ƒŽæŽ‹•‡ ƒ‰‰”‡‰ƒ–‡ •–”—…–—”‡ –‡•’Žƒ–‡ ‡ˆˆ‡…– ˆ—”–Š‡”•‘”‡ ‹•ˆŽ—‡•…‡ –Š‡ ‰”‘™–Š ‘ˆ ‰‘Ž† •ƒ•‘’Žƒ–‡Ž‡–• •—„•‡“—‡•–Ž› ’”‘…‡‡†‡† ˜‹ƒ ƒ †‹ˆˆ—•‹‘•æŽ‹•‹–‡†
•–™ƒŽ†
”‹’‡•‹•‰æ„ƒ•‡† •‡…Šƒ•‹••ä ‹‰—”‡ sr •—••ƒ”‹œ‡ ‘—” ”‡•—Ž–• ™‹–Š ”‡‰ƒ”† –‘ –Š‡ –‹•‡ †‡’‡•†‡•– ƒ‰‰”‡‰ƒ–‡ ˆ‘”•ƒ–‹‘• ƒ•† †‡…‘•’‘•‹–‹‘•ä
‹‰—”‡ srä ‹•‡ †‡’‡•†‡•– ‰‘Ž† •ƒ•‘–”‹ƒ•‰Ž‡ ˆ‘”•ƒ–‹‘• ‹• ƒ ˜‡•‹…—Žƒ” –‡•’Žƒ–‡ ’Šƒ•‡ä
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vä ‹•‡ †‡’‡•†‡•–
•‡ƒ•—”‡•‡•–• ‹• …‘•„‹•ƒ–‹‘• ™‹–Š
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昋•
•’‡…–”‘•…‘’‹… ‹•˜‡•–‹‰ƒ–‹‘•• ƒŽŽ‘™ ƒ •‘”‡ †‡–ƒ‹Ž‡† •‡…Šƒ•‹•–‹… ‹•–‡”’”‡–ƒ–‹‘• ‘ˆ –Š‡ ˆ‘”•ƒ–‹‘• ‘ˆ ‰‘Ž† •ƒ•‘–”‹ƒ•‰Ž‡• ‹• ƒ •—Ž–‹˜‡•‹…—Žƒ”
’Š‘•’Š‘Ž‹’‹† –‡•’Žƒ–‡ ’Šƒ•‡ä
• –Š‡ ˆ‹”•– ’‡”‹‘† •’Š‡”‹…ƒŽ •ƒ•‘’ƒ”–‹…Ž‡• ƒ”‡ ˆ‘”•‡† ƒ– –Š‡ ˜‡•‹…Ž‡ •—”ˆƒ…‡á ‡•’‡…‹ƒŽŽ› ƒ– –Š‡ Œ—•…–‹‘• ’‘‹•–• ‹••‹†‡ ‘ˆ –Š‡ •—Ž–‹˜‡•‹…—Žƒ” ˜‡•‹…Ž‡•á ™Š‹…Š „—‹Ž† —’ •‘ˆ– ƒ‰‰”‡‰ƒ–‡• ‹• ’”‡•‡•…‡ ‘ˆ
ä • –Š‡ •‡…‘•† –‹•‡ ’‡”‹‘† ƒ– –Š‡‹” ’‡”‹’Š‡”‹‡• •ƒ•‘–”‹ƒ•‰Ž‡• ƒ”‡
ˆ‘”•‡†á ™Š‹…Š ‰”‘™ —’ ˜‹ƒ ƒ•
•–™ƒŽ† ”‹’‡•‹•‰æ„ƒ•‡† •‡…Šƒ•‹•• sx –‹•‡• ˆƒ•–‡” ‹•
Žƒ–‡”ƒŽ –Šƒ• ‹• ˜‡”–‹…ƒŽ †‹”‡…–‹‘•ä …‘•’‘•‡•–•á ‹ä‡äá
—‡ –‘ –Š‡ ƒ†•‘”’–‹‘• ‘ˆ •›••‡–”› „”‡ƒ•‹•‰
ƒ•† –Š‡ ’‘Ž›ƒ•’Š‘Ž›–‡ ƒŽ Š ‹• ƒ”„á ‘• –Š‡ sss ˆƒ…‡–• ƒ•† –Š‡
…‘•ˆ‹•‡•‡•– ‘ˆ –Š‡ …‘”ƒŽæŽ‹•‡ •–”—…–—”‡• –Š‡ ‰”‘™–Š ‹• ˜‡”–‹…ƒŽ †‹”‡…–‹‘• ‹• Š‹•†‡”‡†ä Š‡”‡ˆ‘”‡á –Š‡ ’Žƒ–‡Ž‡– –Š‹…••‡•• ‹• Ž‡˜‡Ž‡† ‘ˆˆ ƒ– yäs •• ƒ•† –Š‡ †‹ƒ•‡–‡” ƒ– tu ••ä ‘ ˜‡”‹ˆ› –Š‡ ƒ†•‘”’–‹‘• „‡Šƒ˜‹‘” ‘ˆ ˆƒ…‡–• ‹• •‘”‡ †‡–ƒ‹Žá
á ’Š‘•’Š‘Ž‹’‘• ƒ•† ƒŽ Š ‹• ƒ”„ ‘• sss ‰‘Ž†
•‹•—Žƒ–‹‘•• ƒ”‡ ‹• ’”‘‰”‡••ä ‹•ƒŽŽ›á –Š‡ ƒ‰‰”‡‰ƒ–‡• †‡…‘•’‘•‡
‹•–‘ •’Š‡”‹…ƒŽ ’ƒ”–‹…Ž‡• ƒ•† ˜‡”› •–ƒ„Ž‡ ˆŽƒ– •ƒ•‘–”‹ƒ•‰Ž‡•á ™Š‹…Š …ƒ• „‡ •‡’ƒ”ƒ–‡† „› ƒ ’‘Ž›‡Ž‡…–”‘Ž›–‡ •‹…‡ŽŽ‡ †‡’Ž‡–‹‘• ˆŽ‘……—Žƒ–‹‘•äv
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