lu -'1 a · abstract·.. ~,,- j oi--1'.. the fluor~scence, and phosphorescence.. spectra...
TRANSCRIPT
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by
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A l'hcsis )
~~bnittcd to the 2chool of 4raduate Studies
i~ 2~rti~1 fulfil~ent of the rtequirements
1'or the d~bree
~octor of Philosophy
c
;"c;,iaster University
.,.ay. 1976
[ HAL V!DAR SINGH 1976
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The LUL1111eSCenG!l. '.6£:Pe~hydro,;' Deutero,. and Halo-.~ . ~. ~---:. ,'~_. - .•• ' ': . , ..'~'~. ,_•... ' ~ ' •. -c' .....'. _:
Pl)enyl<LciltYlenes, in;'Rigi~ '591utions 'at~77°ic, ' . -. . ..: .. -~ '." '" ~.' '.' .... -
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AUTHOR, HalVidar 3-ihgh,' iL~c,.~ - . '"
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(t.i~i:.:ei=ii~Y<lr Guyana)\ "
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ABSTRACT·
..
~,,- j
I
o
--1'.. The fluor~scence, and phosphorescence spectra of
..phenylacety=!-ene-H6' ':'D1, -D:S and -;)6 as dil1ite (10-Ji'i or less)
solutions-at'77°K are'reported.
Vi-brational analyses of the fluorescence al'1d phos'
phore!;cence spectr~ of these co~pounds-in'polycrystalline
m~thylcyclohexane indicate that the geometries of the emitting
singlet (Sl), and triplet (Tl) states are. different. The fluores
cence spectra are interpreted in terms of a we~~ allowed com
ponent and a strong forbidden one; the latter based on one
1't~t.,"
't > quantum of non-totally symm~tric b2 vibrations. The main
progression in up to··five quanta of the ring breathing fu!lda
mental is ~xplained to signify a planar, slightly. expanded
regular ring geometry of Sl' The phosphorescence spectra show
a relative~y long progression in the totally symmetric c~c
ring.st~etchingmorjJindicating a Planar,~on-regular-hexa-
gonal nng in the ~ sta!e,' .' . , . . '
Polarization of the fluorescence and phosphorescenceo
spectra of phenylacetylene-H6 in a rigid glass at 77 K are ,
used to assign the orbital s~etries of.the Tl state as well
~s.the s~~etries of the major bands of these spectra.• G
The phospnorescence lifetimes of -H6' -~1. -DS and -96
in rigid glasses at 77°rc sho\'! that deuterium substi tu'tion for
the single acetylenic hydrogen has aloost the same effect as
deuterium substitution for all five ring hydrogens in altering/
iii
,
[
theradi~tionlcss cteictivaiion of rl' These r~su~are in
terpreted u~ the ~a~is' of a curre~t theory of radiationless, ,
transitions.
Th~effect of halo~sub$titutton in the ring on radia..tive and non-radiative rates is investigated' for seven mono~
halophen~'lacetylenes;'The: phosphorescence lifetiraes (in'l 0- >',i(
.glassy solutions) decrease mar:-:edly \'lith incr~asing mass of the
..
halogen, and the e~ect is greatest for the nara
H~aV".f atoiTl perturb~tion affects the J(dfl values
nosition.. "
.... , .
'fu~d 31 ~30 absor~tions'o~y slightly. Inter~ysten crossing
yields are also found to increase with halogen mass. The
vib~t~onal analyses of the .phosphorescence spectra of the
halophenylacetylenes (in ri;id solutions at 77 0 ;C) indicate the
presence of ~vo subspectra. Subspectrum I consists of the 0,0
band and bands due to in~plane nodes (mainly totally-sy6metric)
wh~le 3ubspectrun II arises from out-of-plane modes.· 3ub
spectrum II is found ,to increase relative to Subspectrum I
•with halogen'substitution. Polariz~tion measurements of the
ma~n,ba~ds ~f the,phosphorescence spectra are ,interpreted in
terms of contrib~tions fron several spin-orbit mechanisms.
~.
--_.... _.
iv
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Or.1~. ':.
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fino.l draft· or thi~ -chc~') i:-:,.
'contrihutcll i'1 .
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Introduction , .. -[- ..~ .
Theoretic:lJ.. .I .I
CIL>\?T:c:a 1.
Cj{,·!,i'TZR 2:
TA:aLZ uF
!I,Ii
- I
CO;;TENk3
1
·•~•
3ections.
2.2 Cl:tssificstion of!Zlectronic 3t:ltes ....
5 ,y
7
8
10
13
16
18
19'
20
2:)
26
27
:'0
29
31
1:-.-3:'
36
... . .. . .... . . ...~. . . .. . . . . . . . .
.. . . .... . . . . ... . . .. . . .. . . . .....
Polarization of Luminescence .
Assif3T1lller.t of Or'tli t~l 3.\TlT:Ie tl'Y .
3pin-Orbit COUplini>' , , .
Inter":"'.al Jlc:lvy-atom Zffect , ' ..
;)euterium Isoto::,e :ffectr; .' ':/' .
:nviroru,le:lt:ll 2ffects , .
I
32;~111ctry classifictltion of the"h '11"1., ",o""!l~ne'~ (::' ...... ,~ \·l'\.,.~ 0",\'" nIl'S).... t • .J _" .......... c .....· i..... l".~\.~ •• '-' u\W.~.~~- t;: •••••
2lectronic Absorp,tion and Emiss ion .....!
The Theory' of :Slectro'?:ic 3uectr3. ..... "I •I
~he Fr~nck-Con~o~ ?rincinle ~./. 4t. .Radiationless' Tt.msi tions in Con-d d " d' ! .ense ,.,e la ·.. , " \ ..
Experimellt:ll Jctails .
301vents , " . " , , .
(::ampie ?renan. tion .
App:lra tu", , ..
2.7
2.11
2.4
2.12
2.9
2.10
2.8
2.6
2.1
2.;
::<?erimental .., 3ections I
Chemicals ..
, 2.3
3,1..3.2
3·3
3.4
3.5
•CHr\PTE:1 3 I
,
vi
Vibr~\tiol1~1 ;~n~1::~~0~~ of '~1.~lor~~~c~1~~
":;I'Icctr:.~ 0" -i' •••.••••••• : ••• , ,
..!: 1
41. . . ".
. . . .. . . . . . . . .. . .
~U;;1ine::;cc:1ce oi' rerh:,·J.ro :::'.11 Deutcr:::.tcdPhenylacetylenes .•....•...........•....
:ections:
Gener~l ..I, .1
!~. 2
l !~ . 3
Jiscu~~ion of the i·'luor~.:cc~c2 0~
i']wnyl:,.cet:'l'-':1e ......•............
/1
L' rr' ....: Vibr3tion;11 :\.:1::1y~~..·,~: .Jf ..l. >.o~:"~",o:·,~.;~·, :-'.cc
3,lectrj .
Ji~~cus~ic.l __,~' ~]):: _;;O_~~<1'':'''l:: '. \ ::,...,..):'.r'hcnyl:lC'L'~.:·lcr.c .
-'
.r"hG;·(;·1:1ct:-:~,-ler:'2-~~.~,...•. ... .. .. ... .... . . " ...•
JeuteriLu::' '::ffect O!l th,' l·ho:::']Wl'·.";Cc'llCc'Lifetime 0': .L~:len.;.·}_:-:("_:"'"l:.rlL'lh·..•••••.•.•.
I
"
I, , ..
I
C]l.\PT~? 5: L~ine::;cencc of tile _"11o"'''·::,d::r.L·t::.lc'''c'': ... 11
3cction:
'rhe ":;ffcr.~ 0f !~L):l\", - 1tO:,1 ";t;~'.- ti tIl t i0.~ l1;'
fdV )' / l'
i·hosphore~c'-'l1ce Lil'c·ti::1L"· (. ~. 11
Relative ;,atios of til<? .·hOSll;~"'C.·,,'.·to' ;;'luore<c,cencc"\ Yi c'1 1 r-- • "-'1 1.11• ..... .~ _ .L:~ •••••••• 00-0_ ••••
5.15.2
5.3• 5.4
:':cneral .... ,....... ... l'
...
5.5 Vibr:'ltion:"!.l "nal:lsL'ccnce ':I.h-,C'tra of t)h~
1 '1yf th1.2 ~ hO~~~"1h~I:'L'<-~::~ lo.\ih"\;1<:1"'lc\"\t.',·lt,t~~·:·
5.6 Interpretation of tl:L' fho.::~)hol:t"'.~(,\"\l:('~'
rol3.ri::':lti.oll~) : ------1'
CHAPTi::R 6: 2nviron..'ncnt:ll 2ff~'r.t~ 011 the .ull:Hllh-': CC,l('l'
....;pcctr~:l.. : .. 0 •••••••••••• 1
1
KZFER2NC~":
\".u
Figu:!"e 2.1
Figure 2.?
Figure 2.3
Figure '3.1,
Fi.::ure 3.2
Figure 4.1
Figure 4.2
Figure 4.3
Figure 4.4
Fi£Ure 4.5
Figure 4.6
,FiGUre 4.7
Figure 4.8
?i.:::ure 4.9
Definition of~he coordinate (x, Y, z)"" f C un,!!"" d h C .. C~ .-a;,::es ,or 6"5" ~ll an -:- 6t'4- -Cn .••••.•••.
Schematic enerGY levels with radiative andnon-radiative in~ramolecul~ encr~y loss ...
I ~
Franck-Condon and stationary electronicstates ~ - .
5loc:c diagram of :::pp:lratus .
Sensitivity cor,cctiQn curve of ~hoto-
multiplier-rr.onochrur:lil "'.;or - .
Non:ml vibration:; of monosubstituted. benzeneG(schenatic) ...............•........ " ...•....
The 'Fluorescence .3')ectrum of 10-31" ::>hcnvlacetylene-H6 in P8~YCr:ist<:lline methyl--c'yclohe)~ane at 77 -.l,. •••••••••••••••••••••••••
, -4,The Fluorescence Spectrum of 10 r.; phen~'l-
acetylene-Dl in '')8~~'crystalline meth:,l-cyclohexane at 77 l\ .,'The Fluorescence SpectrUtl of 10-\, r>hcnylacetylene-DSoin polycrystallir.c meth~'lcyclo-
hexane at 77 K.'..........................•..
The fluorescence Spectrum of 10:4~; vh0nylacetylene-l)6oin polJ'crystall·ine m<;lthylcyclo-hexane at 77 i~...........................•..
The Phosphorescence Spectrum of 10-3;" pheny1acetylene-H60in ?olycrystallir.e raethylcyclo-hexane at 77 :: " ...............••.
_L;.The Fhos1Jhorescence, ':;,)ectrum of 10 h: ;1henyl-acetylene-Dloi:l ,ole-crystalline nethY1c,'clo-he::al:.e at 77 :: .
_l~ ,'rhe E'hosphoreGcence ':;!'lectrum of 10 j,. ?henyl-2c~~Ylene-l)So~n ~olycrYGtalline rnethylcyc1o-he.,~ne at 77 ' , ..
"
The :'hOf;"0horc~~C2nC'c .31"~ctr\.~r.: C'f ~C-"':,_ ',):1l;)n\"l-
::.ret':le:1c-J,~, in 1)01 '"Cl":st:'.J li:~0 metll\'1~"'\'('1~-, 0 ' " • .11l':':,' l\~' :\ t 77 .~ .
\' i ; 'i.
15
JJ
51
51
•
Figure 4.10
Figure 5.1
Figure 5.2
Figure 5.3
Figure 5.4
Pigure 5.5
Figure 5.6
Figure 5.7
- \The polarizations ,of the fluorescence,and phos~horeGcence ofo~heny12_cetYlehc
in a r:i.gl.'! class -at 77 1\. •••••• ", •••••••••••
The fhosph0F;escence 3pectrum, of 10-3", p-F.%CCH at 77 1:; (J,) In trans-l, 4:"'dimethylcyclohexanc. (3):1:n u ri,sid c;lass ......••.
'," I
, 'The Ph06phorescen8e 3pectruI:) of 10-311,
p-Cl % CCI, at 77 :~. (A) In tr:ans-1, L~,_
dincth:rlcyclohexo.ne, (D):;:n a r:iGid;:;lass.
The ?hoGp~oresceBE:.e 3-6ectr..unOfl0;:;:3J,;,
~-i3r t CCl: at 77 ", '( A) In trans-l, -,C:imethylcyclohe;~2.ne. (!3), In a riGid ::lass.
The PhosPhor,Gcllnce Spectrum of 10-3;,: 'p-I %CCH atJ77 ;~. (A) In tr:ms-l, 4dimethylcyclohexane. (D) In a riCid zlass.
The PhosphoresceBce Spectrum of 10-:\.,m-Cl %CCH at 77 K, tA) In methylcyclo-hexane. (B) In a rigid g12.ss ', ' ..
The PhosphoresceBce 3J?ectrum of 10-3r,;m-Br %CCH at 77 K. (A) In methylcyclo-hexane. (B) In a rie;id ~lass , . , ,
• 1 -1The PhosphoresceBce .:>,?e~trt1m of 0 -t,;o-Cl %CCH ~t 77 ;~, (A) In ~ ri.,hl :'b!';,~ .
99
126
1~8
12?
141
1 )I '?- .,-
"
.... .d
O"--"" '" •• ou • .-' .-'
.,' ...
, ',•\
/•
2.1
LpT OF 'rAi)LE3
,•
3pin-Orbital I;lixing of Singlet arid Triplet 3tates
1J
__-------;--:----'---,-e.----4.1 The Symmetry, DeSi~atiOl1and...\pprO):imate:De~'- '
cription of. the Normal Vibrational i·.lodes of' ~
. PhenYlacety lene-H.6 · ' ~ .. , ...• , ., ,'..- l' • . . ' •
4.2 ~requencies (cm- ) of the Fundamental Vibration 1'I.lodes of ?erhydro- and ::leuterated ihenylacetylen'~sObserved in the Flourescence (1'), and i'ho3chorescence
, (P) 3Be;ctra in p'olycrystalline i,iethylcyci"ohexar.eat 77 i, ...• " ••••......•...••.•••...• " .•...•....•
44
47
4.)
4.4
Vibrat~onalAnalyses'ofthe Fluores£~nce ~pectraof 10~ J,l Phenylacetylene-;{6, ane. 10 M rhE'nylacetylene -)1, -;:) 'i' -311' ii1 ,,'ol:;cryst:llline i<,e th:'l-cy~lohexane at 77 K.•.••.•..••.•.•.•. , •••.•..•.••••
Vibra~~onal Analyses of the .i:'hos:,ho!:!lcscence 3pectraof 10 i,I Phenylad'etylenc-il6, :o,nd 10 r,; l'hcnylacety-'lene-::ll' -;)Cib••-;)6, in Polj'crystallinc lIiethylcyclo-hexane 0..t 77 .\. ' 0' ••••••••••••
52
76
4.5
4.6
5.1
5.2
5.3
5,.. ,
Ratios of the Intensities- of the i<.ainVibration..'llFrog~essions Compared to the 0,0 Gand in the £hos
,phores,?ence 3pectra of l'henylacetylenec at 77 j~.... ,107
30me Properties of the .3 0 - Tl :md 30~'ri 'rransi- 4tions for Protonaten and Deute~:J.ted~jhenYlacetYl:nes109
. "'" \.'30me Triplet and Sin[let ParQIDeters of the -~~lo-
Phenyla~tylenes ' : .. , .. , . : ..,. , . . 11 i f
Fundamentals observed in the PhoCnhorescencc '::;nectl':)·of the Para'-Halophen;:)'~cetYlene:;.:.. , . , , , , .. , , : . , .. , 1.2 J
Vibra~~onal Analyses uf, the l;hosph~rescenC'e 3i',:,ct:-.of 10 i'l Para-Fluoro-, .-Chloro-, -r,romo- :ene'. - H,jO
pheny~acetYlcne' in l']-'(;1,,·-1, 4-Jil:ll'th:dc:, cloh"~,,':1""t 77 K " . . .. 1JO
l·'nndnmcnt.:!l Vi.br;\tll..lll:'{ ·~'·,l'I'h':~ \,lhd'l"\'l'd ill tlh'l'h0~phol"'C.'{'~'l\Cl.· ~~'l'\"l \'! 'I..'f ~II..' t:1,-ClllOI"O-, ,~-:;~"'l:h'-,
'\nd Orth0-CjllorO~11"'11,\1:H'l' t~·l('t":'." .. " ... " ... " .. " .. '" t I~l.}
J
5,5
6.1"
;
Vi!?5.a"tional .-\.na.l.yses of the ~'hosphorescence of10 .•; ~-chloro-, r.;e"ta-brono- anC: Or"thci-ghloro?henylacc tylene in •..eth:rlcyclohcx2.nc at 77 ;-c •••••••
•.'
C . f·h 0 0 - - '" ·h - ."." .o:np~~son 0 ... e '. ~~'"1.G. .1.0:::- e ..;Jo - ~l .Lra.ns~-
tion i:1 so:ne benzenes " .
145
171
,..-
~,•
~Iolecular spectroscopy dc~ls with the int~r~ct~o~ a~
,'
electrbwa;:netic .radiation with ::lolecales.
e~ission spectroscopy Give i~sichts into the cec~~t~~ 2~~
~ature of the ground ~~d excited st~tes of ~olecule~.
escence is lisht ecissio~ r::olecules
or ultraviolet liCht. £'>.0 to 1:l:::i:;,~::; ce :"'.C C
on the chenical cOr:lposi tion of ~}';.e c::.:' ttinc ~~.. ::;~e~ ::.:-.20 of t;";-'-.'
, ,ttprocesses, whic.'1 takes pla~ after tl1c 3bsorptio~ of the exc~:-
ation enerf:Y. These processes ~r0 closely associ~tcJ
•,that result in photocher..ical reactio:1s,
Benzene and substituted benzenes have ~ecn s~b:cctc2
to intensive spectrbscopic research within rece~t ycar~. :hc
absorption spectra of phenylacetylene-::6 (C6E Sec;:) :-.::::c O;:'C:.
stUdied in the near 1- J anc fG.:- 4 ult:-2··:iolct, 2.:1:"r:lrcj) 2..:-:.2
~icrowa"e6 '"' • reel.ons.,
EI:1ission in riCid sol',ltio:1s "";::lS i~~vc~ tieD. ted b~,' _h:..l:'2. \"ll~ V~-)
The deuteriun substi tutcd tl.cct~'lcnic hydroccn de r i V:l ti ve r
acetylefle-J 1 (C,~ii<CCJ) ',';:l'- "tHeli,'::
ques 9 : Kine and .3010-1:: l'ccently
-- ; n r,.-_, "-.~.~~""'_""_~U
to include the rinc deutc,~ted phe ny 1 :i.e!? t.\" 1eilC -J [, ( C".J c,C C. ~-
the completely deuterated phc:1ylacct:,.le,,~- ",Cu-lc;:::CJ).
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