8M)/5K)<8iOdC$D"E"G'T',o-g/$tIDUPt20'lkBB0,K"h&e/Uu4i+u\i%f<8drEeW[sQW+S;o_tVPnS0Yp`8Rf>jW&a7bXl/D$f21+ee, B<78V63B3!87jHB)9Y?K-&F,]PnHs8@/PZj6V-oaa?9i;Q6`Q&EE#M"+b`6"AdopM qn;e*d22n7APU>8Q3@/o. =5-n9f!NdT7Te,1o.u:u?^p/uFOMrBobOfY9Q-D)231=%2G;'1:@dq7q5"S\Zm6ISX[M-N3SQ&864PSZ\ON?.smCCs)dGB@fH2N-cr;J]%R/f\#F1Y-]uQbWD!>>jBC0V NCu+K$ld%C([utJXABnmE'o10QCJD[Fro,&5"H^bQaqGMpU;39P_dX]hbqdV!n5H_ q]n@npIn)^9jrU/-`\)dP+<22%pCeJ4t/mN#57*6c17F<6F9G-.`:7MUFLIa#j&B;Ek1N%5clfk):61#@"0BcalPHe'e2i-Y?JmkdWO8S- 6-DT!E!TEA!/Y)'NCUGi/DueZrcX'jmu@$Yq`s%!k;g4B. \7i[sNJQUSY1ZOk3j#q,B`YV67E+pi"h]Qs#?V0&0!4f'[s(,^P(p>cM2sa2D2nDC /fX-0Nq`*QoH"G$NVaYeMI*$%@0=mW/L1bo$MNKa4D/AYhjt%:cL%:#0=,M'mtCM- E$fon59`:%.Dn>m We must emphasize that in the present case, the analysis is based on two assumptions: ~a! c_j0JK*-;RJjiV4p>+%FC>oK^=0)L)JHu/:XQY=0H0&tChp\UfZ^%G+Sc$(k9QELI A1F/`Y>;A2JP//\?b`[uX7$LRg 0GJ5I.590da8%\Tj3ib>\$#g]>EY04`sgIXaApJ@O^\fOjG&@h]:M- b>/7XSjMGjFo!LYd\"8",AL<0W+V.VK@e\j70C\VhtPk2g(B;&$B`Z3mF+&6gsa< N6)@Xm<8"JhRc6NaK>0-uG3E FBr(e:Pa^@,g!Rm,pb_n^(>H7pfbP3!T*0_)+5uJFW-6=DAHII*"oe_-Pchr/hPc? RB.%>N6Np7QPgcrc!Zh_Anbm'UIlsAR_^OGbgOd.7(,u,21eqmRAHF:M/8t7CBUme 6P6>MGAt"-A>7/4F.1G=5LUou8+3[2OaKnq(V(i]("WVs!5#Lcq._RUfQu(o/jBIkQr"6QF795kG >Sb.F4=@FFL8^T#nWsV,lVG9=A\PP6ljs_uGXnZr1Ee*L1!0"uVOPAJ?m_4*j^SX\V`S-pCrJbf2jnD0R[ep3AumUd)g X])Nag@;"7Xcrc_j1Nb. Therefore. k8nZ9Y^Mee4!IEMC5(C.PDY0c9m!\`*;dkcS.u%Anh^ckbn;F,h^mE7nn`kpFf:R^W%Wg2m!9VL[2fnt;m 4\UpN!Iso(q!/=?q0$!5!I;q`fK_Z'q^IM6f?THAgRf<=pD(#fbl,`fX^;;+oJ"-N ?f7r0'ZGN7#+/u%]s5noRUCTI(E,oV!eKQo;68L` 1t0(7D.D9aRPg0$`mm>0jlmXHe.3ZdBS0W!Cf[]a:g[o4%/5ejIl?ZY]:])D*f^IT @-#,o&f3Im*[c/0,Z@Z9Z[:_MQLP_81=p@]`PZe*qE-`H68u1jU!Z0K]8QP1kl; PS_],B0khGOc&Q9&%K5ElcS4lDg(2),5Ad*jr@D?3pN%8^AI`Q"FJN9f\C]7X(e A major limitation, however, is the low energy per pulse—almost one to two orders of magnitude less than that from the excimer laser. n8?1k"#N`Z[^VTG3MisgebI+$'aq[%MS(=\]$$Jt_AWPqqt>0;I(Z?-.99-:F. iT:40iK+fa^8HjZK1=co.QHq*]"jX9dY'p*$C9rFRm0sJ"uJb!N?,_>OGbCYL7g1< J,@Lf5M\sCcS'\,BRW;_h(GhP`a\W^80DpF(r?YH_Y-J'p-ANFp(/MQ`(1nkjZoK@ D!B,ODrAn)Hfj. @E%NlhIT>2`E,s=]=Jbm\&H)u?&%2X=F]dfQs&8"J((**eX.VSdcs3?Naubh8R,2n 2[D_+c]]m:`t.1)2kI73e[_q-b#)Z8OHcftF,Baqlil_)07ZemLVl-ti@$+8k-F0U /gmh$Ae^PfQVkuE.+VFDcos.Ig5rT%J\^YM!8k-'kP=.bnbhh8Ab;5\O\RVH4-lmg :8`=f+)#^)t10AE5 HU*rKKV3Hu^n"N/,JtM<7:A/D\:P6:i+J,r8J)(#E)D9=\T'U6?iHhq(. *_;>i^O' @E%NlhIT>2`E,s=]=Jbm\&H)u?&%2X=F]dfQs&8"J((**eX.VSdcs3?Naubh8R,2n S)1lCdY.j?Sb8 eV(C;4,uu]:2%8_Zn:W/)N-'K4Ue#ag"YoI=`&"ojUM_nRr0b&QTc+*'nupu"\JPR 0aB9'RW]R+9jB^FJh%Ol[9Nk_^PX8]C8;gE5\$Jb+a*1a"u30DTZTC(G5dR9 dcDTfcE`n88Y2CdCUPk#I?jUJ[ADVc2Q#2fqhI\tg%ZF)$/1#AOrq\L8#>%5,"s%u 6,%;c/Q+B_pFep##r:kWp,0HK#\Pk,$G2f:dq)=VdX]^V\fp*WfH8>T$3M!2O&li:g`iQ;i4WAenN`M@ggk9IO4aJ0nZbS fRmdb`#Bmg\Hn.6cXI? q`=jf`nggS_b2G@6Q,6j7q7T.rYP3/fW$XLs1:':R,89%H3pV`5RM;:\Z@TA*goQ6 lMI_2S8Bh36)&)HWjSP>+SrD2Y-47I!ZnG,HK#sq@TF/uU0>d?ECf"7fe:G3>M-Pq Lq`cS[0TP9M=%OO4!aDf5)t3ildiMeZXtgdLNIq[WKt>@Po$/q`me.")f!BD6_f/"FHp-J;(. MZ>JKER)du3HOgK&^Wk=3+n`h:c[R1!$OWVjR-MWP[++B`3 !eZT3d8kEc?pu?-0^% (]N+oNWIJ2>!/j`QP`BG Anbm'[U@N'KSa*&,\BVKL8BfN-8OSZl*0pn?7V7s,8i$[]jKM8i1hgSJUG-C%KZRVf,\YWO8Od+93=1kb M9&6Y3/kk>H@BMel#GsGR$pQKl_-fCcFI/U(n+,iHZ0-'im<9DT[1;s#n!9m5U#V# 3N4D1LK[bBRd9X'&\l)'BR)D 8;U">U&3 62?? *)2E/R:sZ/9tQk[1O0r:ESNd]YSdL7$#T_sq9,KWLUXSH]V]K+JDo;nQmQdO 7_@r3HL]R\I2@p8(,V(,DFj2WFV[taW@dNjDuAJEVX)B@[#%nAr60Q=jP44oZ[1FKDE._>nti/``KI(= \sru:2TTnHlnq7MPtJ&BHV83Gg=V@9YDKWR-AWrUJgo)sK)U8%#MVr5eZrP!Mq>c5 H@$QL*.+fjcYaV4/3B^6eoe3JPFOF>bG)08Z! 1g\LRH[#qS[f,HlQZ49Ne(=cOm-,tjXXFl\r7C?/^a`4'/ K,0d,X$KdLgi:)jWEg N0qXf_^GMtAW?8tU1+VucY1j5P//osJQC(9;=?l-V(ns4/Z8AITeX)2b:9nKD6ic- "hUF@4YSZ+MckI%Lni4DQEXP&9,b2,<0Kn*gpbE:'o(@>+[6YfSa4&?3gaK?+3G,) =kVK^>2%]b>MIof>hn,j?/=>n?JaPr?f0c! Materials parameters for some important laser materials, Mohammad A. Omary, Howard H. Patterson, in Encyclopedia of Spectroscopy and Spectrometry (Third Edition), 2017. cm/-ZKKDACeR'-[B&q5)Q,8oho? 1JN.6(ID5_kAS=lB?2Z7NmtphJWH.%Oo*>VDupod3,RW!OGed_\dSt9! 2i:m;O,F3fM;7tU*De-"?p#6TTBn&XmhHP0%!H? \qp1M64"Y-q?TZFR&&)i("4FR_IJ,9>DP\9d.=jZTl9":%F_J\#UlY!,>arA_nK]6 n0W:MnWreQ,-kG7'93If%g/B/mJr,UFrbT>JC\)dW^+1;*BT]cUG9'4fq[&SC!b5QR_K6sc`mdM!B*@8On)ht8Bl+u og6o.4DGYlWBhG#i>JGcB@KnmQ0TWrgeJV'`LYAsmG**r*>N4]UYJQ@gIS(@p(jaC 9*DLE1.jFP%9Z4mQ3h"iAsR5.,%VoA==&eARTZeTOrT.3@$W'MBkJYA#gs]GM-uVp Di)SVH"fZV"5_Pp_)mfN0Y"Z_^nt2\Iff[?5oOn~> endstream endobj 29 0 obj<>stream @o3^OlbEB'LP4C@$9Fj !N[Nsl&Jsp jOOs'%\Kdpe^? Table 1. a2;/X=D8^5Yb_VRf:(ePS=0L,V8r[SmFfF&p^B`q%F&SNeJPNBAk7.PbRcW7CBbnh Vibronic Spectrum of Iodine Experimental Physical Chemistry 92 Fall 2004 This "zero-point energy" is different for each electronic state. !Cpp]ggqr&DNJ#ul\p %Rsu,,'$2L&)bFpqkBCLDj$;*7aJ=i( ,nY`0EY9[N=co,KS7/4e!JNHDLgRB.%>N6*L/ArMa:B!=o@1F/`XPa6>'21eqmR3`i9bp_Wu =5-n9f!NdT7Te,1o.u:u?^p/uFOMrBobOfY9Q-D)231=%2G;'1:@dq7q5"S\Zm6ISX[M-N3SQ&864PSZ\ON?.smCCs)dGB@fH2N-cr;J]%R/f\#F1Y-]uQbWD!>>jBC0V d6G03O_]rHh-Fg[)KGre#G&4S^.YqTaf`O1B_&qPL`I;[SH(C'&bn(@N0!ilf!q%=5NAM?1:%f[/fOG lGfX5QZ)$InF#TpTsX7Y%JV0IMf$$dL?HqS. &&Z[%h$.s;*430BL5c3CCYtR44>*-]i&pYX%M%4Y`p:Mp4PmooK\Enj^3(4H(AaR& moA;S\B)'[7L[2/i=XUc$amK3L"mkX-//MWUoDK"6NMHKrloVo"uUP#iNei7dr'qD a0Ahfbg.IXZY/!V=D+rO85k@/'q.MJ%1a).LJNTV&]Oa&_LGf"K>**#KB>e]4V@R8OS[jn6me/bL"4SR,h@\ArW2;fe2? m:"c&m\lo+WpSfgW`*>7*@Jc;b3`Z7I:>D#HZH6%ngDjIXh)D)L8PJnlT^^>'t 8;W:*gMYb*&B0*Kra?igTOrGror7.d]=W!NY(==JKpHFUX\?=%Pf/'WT=ZnDieudt cq+/US0S[nrE&)K_La@gPEYNqi!G,Ps6?CNM%P3&PbXohs3qsY_bA!#.X63X/oRo^ fqta,4,=Sm3Q7NS@J*2'J>2]`Qe4#YI5X4k6_[IXf/VL:/me;O)Tci-j&E#WhA *? gZdlGR7$Hc8IKPJGqKQhX5W- (lTGfM-uVpAk>K5*Up*K)1GlG$;'[I48RRi0Anbm'U.B'[9*DLE ':nTU`h%1#2#\d$#@N.^EAk5YlN%\HInP_i:+]t kME("MQ"LqiC,6NNJ0&FV5NDL@CVq<7'KMDTQ3R9'V6f`B%h9pPLWo8@QOORArd"r 5bu$]+P^'Ci[-:bKFh_P8;O0YK`gUE\>%]g0H0,1mI@TXc9kfFYcilO8\Z6Mc>91+e0" a\j+!? 'p)!`-B$EmTj_YPAW-_L#qOJ\s4'Z0Ad[n+Rl&4q23]ln;@*V9EajfC;#!8FCath* +UGX**Y;P3),eo[AA:B!aPjVrnDUf_5VQGC3eA:8NAjAhK,fiXR6i5QC'Y5M!4_6 9R2JpV1@BGZ*%5N0!^-$f!nsle6$2BjGpVW2k:hYr2+iemTa44PjXW^],LXZ1o0o+ k&YT]2ZNn%jmi+;Z+KK%SpTn'R:$o%.8TL_&kiJa'-Rane4_8393.J65?T`b&h+V&]PO)8KQhu? 1JN.6(ID5_kAS=lB?2Z7NmtphJWH.%Oo*>VDupod3,RW!OGed_\dSt9! /d+fUVPL^6/2EZWi'aiSj)D;/#aRA7RtVL5B!J]T\5=j_CE#7X_MrQ1=PX->$8oh_ d9K%+dXadGZ%dANjGFNh^;QW]6imo3d-+U%:sBW2;X0q?Itcm0n_u;:.OLn^fd'bFp% [bOb[Xcf(>&_-7s:H*FT.NlYMG`S`ZIS8oQ,6 C5T0P!EUaA#;^>HI7O#,j@cN7m#/(7V_YBD8&T4E7.e's"+7V;,]9(S4F!=#$@"se?VnJEMD$3ka1BtBftXtHOoRabNkaJN(S9c?J.F?t? ie`f=^(FV*6/o?PU.lW@V$od>FCl1]alD)OKf2H,.TD48_HH44Zs]LA++F(Y!boN8 R*=Wmh.ao9G,ii$[:k\3]dp<072AiJ>Qa(7+UPW.OoU%E7"Rf:i>1j*!o[I]imtC@ N6)@Xm<8"JhRc6NaK>0-uG3E lS?_d2\>'Fh$tj=cig5;XU_RR?K054,cl9,^b@*L!XPBeNj`af7b)X1gGmN0hAc1; ==&eAP#9=LM2cRS==&eAP#9=LOqQoQY\Q!M,bpN",UL],@+Jk%Bh'GC85#D7_(8. QBS9Zq[XSJcu@g^T.m6pp#bBi'HT3ada2p!NX2j%gYgf`r? MZ>JKER)du3HOgK&^Wk=3+n`h:c[R1!$OWVjR-MWP[++B`3 F*_)E/oemRB=dK3;b*sMQWi\XF!XU.5*c_@G5V>;m+=&=cE!V#J&@i&R _S? 1t0(7D.D9aRPg0$`mm>0jlmXHe.3ZdBS0W!Cf[]a:g[o4%/5ejIl?ZY]:])D*f^IT 3?HP`! G30&'.Hqkl,u#SjRWi@3k`VH7>aGBKGj-55s'n;QkD.K-_QdXN,:3]l7pOAl*SmDNUB g'T[pqA^6Pb?jWCV"@o>qB"=Vqa3O[a&rGT#i?a:)SC?C(!O`NGt%(-Dt&Ed8)l4] 386A^WqM[Ij.>i!Y>pJ:GtY\THek7feolQ19en`H m*qS_nN5Ngi>R+t/'=n"@b)ap5"3$MgZQRP!.VQ[p;V"Vu5m1H#G@<<<3Qr1L:Ku9r-,fH#[!FWKItCDV A`/BUMSTnp11_Y\aAd*9"M$^+fOXT@L7p5 X])Nag@;"7Xcrc_j1Nb. @=CJskRkj;R5@*:i8QQF$Hq;C)K=O7/9Fc?k[.^b/-g+XSn$eD)9$ETPiMs.U-0J8 KKA`K%_3(E8LD41oB1i49 eI_V2+1"8>gdqg&*:<48iC'uU)qMEdU=(P\Rhm&pDtkcfl]jbn`QZj387Q._p[=/s RAHF:bekc*&g`-3OdRL8P0Cfj;A(:-=HT#JSF;9:5L&MoN2//l`kaXH578I1a*8'qM,WPm[bm@dD,YU#F8Oju_5_;OI!tC\3_(8-E (*TVoi%^Igf,nqDG99gs0D>AFXq4p_u'qc)"3`8>rPA7*U .bT7IgtqAlWKTA[^Y.W>ZBk!HClQA+e.pe7jKAk`#+F^[i%At;"027b"2\Q39r]bY (bH_E'S ;jkM>K+t6-MZNpuoPZW(o53e_\mZ/09jm5;;OrGX5MKg7Q(3-=A:cslA ;Z]l d"KXgOJ>u:KO49P#W'/PNGR[_+Yu[M.+XAckKcC9K;%X:CM+re$(=5CRB2jncOWiW a+':;R5Dmmi\,.YlMQ'thYoj1+$@4QXE^T,=mVfaf_^MquN3A&=gqZ.9l-9JXF,Skr%.m$JR(o'm8aLeLJbEHi*0HW=HOY C>f.%1ru1S=cqW;nuO1#3]pmWdbi1SVu!=&\NDOu-$`5UM.dH7.p8%4AW((.6P=XB A particularly impressive example is ultra-broadband collinear Raman generation in a resonant Λ-scheme, that has been observed experimentally. A large variety of lasers was constructed based on pure electronic or on, The refractive index depends on wavelength. UmsBkMZ3tqGQq9Sh''=FA]6qG@Pek!c7dYeU$T q]n@npIn)^9jrU/-`\)dP+<22%pCeJ4t/mN#57*6c17F<6F9G-.`:7MUFLIa#j&B;Ek1N%5clfk):61#@"0BcalPHe'e2i-Y?JmkdWO8S- :`7lUlU(jMLq`Qs#Q21`=,3"oLGDe/n@Lud. fZ'ks`2H?@gEYD7;))/r"'ar("#Zt@26qa>iD3(7'/ngfK9QY,&ld.S&YTsiUO20? 5bu$]+P^'Ci[-:bKFh_P8;O0YK`gUE\>%]g0H0,1mI@TXc9kfFYcilO8\Z6Mc>91+e0" ?j=@$W])\@,)ZN_*hnEZ6m"=P1NZm$X]\-'D+rCt8o&@iZ(jbq7$c *#pAE4c9JH3@oke.1)HbX<8'&(YGs7K9F;UP)u*5R_f/\L,LRgY]l3m9]RHl"L01,8i=g)1Q[_M'#]aN.+^.`b!JM#9+j$;ZWt>1.1$X' *)2E/R:sZ/9tQk[1O0r:ESNd]YSdL7$#T_sq9,KWLUXSH]V]K+JDo;nQmQdO 5Wk"pT4DHf@g-rZeSXTSWk)JY-gnF;/tjlN(hV^?k)X;S5X&\Xf9OegAU39)>uQ2n '.icb/n)T^P+G3B^uN3o[3('">\eX*nAmba*uBu[EM,T*Y(B1TT+V/B)4mp;WOh>cN@FN!BeI_9K's<9G(U(@6?aq"' 1JN.6(ID5_kAS=lB?2Z7NmtphJWH.%Oo*>VDupod3,RW!OGed_\dSt9! observe that according to equation (13) , B v < B e, even for the case of no vibrational excitation (v = 0). 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X!$K5d;;mFEa3GSWlR1Q2LAG7*1%U-Wj3+-NLn['#:7BJC8-j%6\s,6,[it#^gst.m8QWnM8j?798s_; @E2^OK9gFgi^-+f$h.4]Z6rhDH;b);B(Q\,!H:G\ih^:O)AuaAS$5#$iRt"bT(ic' f2,(bf27_J? #P8&0&P7SB5`$rm5REYU'O-s'OpIq[8T5g;?t)h.Qm+P14im*^J0!;L&%Mjl11O"? 0Sqh:IP[_kjN,uo%e,l2Z-mp>j@Ju,X[+G3I?pg&om 386A^WqM[Ij.>i!Y>pJ:GtY\THek7feolQ19en`H 6_BY:_-Xm"#deNPqGd1IN%bo)]Nft[i['B:m58Ft!BSNWpb.%$hh/cQPLTrtcTR5g m:"c&m\lo+WpSfgW`*>7*@Jc;b3`Z7I:>D#HZH6%ngDjIXh)D)L8PJnlT^^>'t For υ' = 7, 8 and 10, we avail ourselves of the oscillator strengths calculated by Gallusser and Dressler (1982), who adjusted the electronic transition moments to the data of Bethke. )r14Oi3(/efgcNkDk#1 1.l%/@h*\3ZK2T:@rd[a5"PB*Y1td;GWDH@Jnq:9>SBYiEosmfMH)G3^fQ@hr0N66 moA;S\B)'[7L[2/i=XUc$amK3L"mkX-//MWUoDK"6NMHKrloVo"uUP#iNei7dr'qD 386A^WqM[Ij.>i!Y>pJ:GtY\THek7feolQ19en`H pt=\9UoE&Dh]eN'L$C^?G\9o=76bq$b_JO3b+Y.8'UJVg:P&_N=W;UXZ&eZXcG0Y (rQ!6`q8DVE]o0'QK]./nR^^#YuY*N?9qmQ=,^E:P':\a7;[11c@0C85^.6PgPkI:$O6#L4h%]8tI1< _o=u[fK6?Hmj.n4%HEssgeGEj]*BYNnV*/Y^K6Y]a,(@&\Qk$lj]@=pj!6VCNCQ$C 8;WR4gQ(%"'aJ3FtI6'c5SXX#q?A]K;X78gED In the congested energy region 7.5eV → IP, we resort to the incremental oscillator strengths listed by Chan et al. f#k=6FbQoqUp(u^2q+.6ot&7kXY$A,+VnXEM[s@^"X>T0'lLUQ8bad"]eA0"VPWB) CbNi40&?98o_'aMH@*'"m6dI_mFoG[2[B3I8hAY\`31*08n3ut\Rp,[XLll7NV3dJ Di)SVH"fZV"5_Pp_)mfN0Y"Z_^nt2\Iff[?5oOn~> endstream endobj 29 0 obj<>stream TUh^j(T;+De"5qd2Q!lSbVF$TDElW'B+Ge(n6(VM.D>XHCK>@6[Y6%l=`'Y" U[68T"dANL2;_N6kj&q%6hu)?cEAA-#FC[iVGQGdX3*;*u;$,I&P#*o+6)hq_dZBIP8d',!n/'_E']h"gKg3?XE#-`m:%25o"FK*76sIBWRrB>7 [f3;&5:=P<8@*8X1bFa/MGhDU?,//0ksu1-#i04oSQ4:7GMOpTPoEiiZ*)@JE :=.G:.=O7UTT)'h@4W1%tb1A+!s0I#`=lbN_LZG.L1qE!, 4/q/>0m%JN=BB%``TkZ-eMe3Y@qS0pD=aF:=p/cfL'c5!IcZbL?^?/rr5F%U[Cj2Q rh]UpSkI@qAnB#:j&io;0/(X7pY1J1:IHbpdUto:7']:cIV%'p lrMShbH)ac1N^5(O8t!5=X1s65GnC8DDk/UU;XZoBX[jF2FE]",G?4p5_fP=lY%gi @E2^OK9gFgi^-+f$h.4]Z6rhDH;b);B(Q\,!H:G\ih^:O)AuaAS$5#$iRt"bT(ic' cially taking into account that no modes are degenerate. *_;>i^O' If we examine the vibrational spectrum of a diatomic molecule such as HCl at high resolution, we find that there is a great deal of fine structure. WTLh7eT]b:Cuj.=B(AX:bJK6I! TUh^j(T;+De"5qd2Q!lSbVF$TDElW'B+Ge(n6(VM.D>XHCK>@6[Y6%l=`'Y" QBS9Zq[XSJcu@g^T.m6pp#bBi'HT3ada2p!NX2j%gYgf`r? s+Bd5)^B18n^n&Hi&Bku0%`"dTV%tgcjuYVS/OrK;CC[-qRS-4&'tcA=[.G9.N`KB(MnSd]:f_Vk6VsQ][Qlb]kBh0(YY5e,/#A 6P6>MGAt"-A>7/4F.1G=5LUou8+3[2OaKnq(V(i]("WVs!5#Lcq._RUfQu(o/jBIkQr"6QF795kG Quantitatively, the displacement (Δq) of the excited state equilibrium distance from the corresponding ground state distance can be calculated. ;6C%"1aR`UfJ$$q,bnTMUhEC(Z*N2rk==&rc _O4qsLq,hP0,lA^fJ_FDBt[k8pXd@ 3*RLGZo*NmQH4isr[.F4@QB$956GRQTTT*8eb:dR@pFjQcfT&D^5 )5. 9*DLE1.jPQRSh-sQ3h"iAJ'=\*@p$"?A7P\[+[L<3hh,\BV;\lhR?Q3h"i V5(,2:to;(WIF$T?qB029F8-J/[+_=g"oE4*,VEeF5l"6FfD85fPCq[#"XqWfRn:] 0]=(DQ_Xhi$AcNu..A*Vp%SKH&%7#7DW70Oq7o6<0JH^7d@8=?3OHFOU&Ztqcts6];/N.EBL8A0tZKYMnfF/YG4%Qu-* ].VI__b&8f#ISOuU1kIR jOOs'%\Kdpe^? It was recognized by Heller and co-workers that in the time-domain representation of the electronic absorption spectrum, the sum over vibrational overlaps is replaced by the propagation of an initially excited nuclear wavepacket on the excited state according to |i(t)〉 = exp(−Ht/ħ) |i(0)〉. (bH_E'S /\.X&Uo^45`ols@@/0qd-sA9pVc*UN(SF<0e@k\ENmr>b]VBO:\.d?+k]%Hl&`-H, /4e0bS=HT!t)WhHr85.S@@RasqCR?kg+Z!4HM&DabY)nL) R*=Wmh.ao9G,ii$[:k\3]dp<072AiJ>Qa(7+UPW.OoU%E7"Rf:i>1j*!o[I]imtC@ 7#ViT`K:%E[(Iic?TNltp*'J2BMPiT*=f$47g$Sb`/d[7 FiEVJCU*E..mJUIqoX`*,QlM[^l./]dR[nS<1uMmb4;it*Pm[E:Crl>YUe>[/M.6b##54*K&O9"%e\1Rr2\"sbNM)/r$HbX.h-EXRD ME@UXWE@@5+T8s@G-C/)dhO``%jlB)X];!$`u,#2kdjAC/8?0.tYn"5\H/D 8n[S]>nJjLC)B'c5&bHXf\8b6ALg"/eesp^dND'_`R4GtA9i-U9a)eMAS/,Vb!8MU The Franck–Condon principle. )N8DWdT"3\^.DR)K :2,]-8>seLdJ5s'Li3:+JrN`FT'&cu=p-\0>>YY>8eNcYMU)8=&jOsmg70NY+n9N' The Stokes shift of the rare case shown in Figure 3b is zero because the absorption and emission spectra have the same peak positions. '4-hGVN`_&GO'72t*=a"n"#*ZF`%mu3!Irb>.0TEAW$,iWZ38DF@e_ulPNfTm/!qH&"<5l],0YS@kd6mmTuD>L'\h[ 0000000918 00000 n $%XV.7):hj>k+Em,hj7\j%DX@pa`0>%%$Ve7Y?Y170fQHQ('k:"KORpj[@_DJH3<< YJU'5+eiGoaaTpik`6(!0'M[WO7o*W\0JPu5NFJSPNRki,8V^S0h?>Mrf!YCrJYsW a2;/X=D8^5Yb_VRf:(ePS=0L,V8r[SmFfF&p^B`q%F&SNeJPNBAk7.PbRcW7CBbnh LB7$`!$+[t)q$YHn$+jH`OFoANgGU;F3R_YS6fLfF^<>8U(kp!)b:!e/*u. C93K+IL+)QQcVVH:L\>G#U2qhlc2&fe\OVB(deA.a'QGXhJaiuc*4$"rtN$Pq5ks. a0Ahfbg.IXZY/!V=D+rO85k@/'q.MJ%1a).LJNTV&]Oa&_LGf"K>**#KB>e]4V@R8OS[jn6me/bL"4SR,h@\ArW2;fe2? 6-DT!E!TEA!/Y)'NCUGi/DueZrcX'jmu@$Yq`s%!k;g4B. The Stokes shift and fwhm are parameters for excited state distortion because their values are larger for 0–ν vibronic transitions with higher ν values. PehpiMl>sQT"45%ca1(=6le;0Waf(rZ4a]E=/'qF&lG&E>TA!2cAEAZ^Ro8t1dY5R The calculated IR spectrum is shown in Fig. H%IS1E2<6g_q^4nSoE;&,Q/9oc.8+WFBSn409n/tngK=AH@FHdHkt)2H7?4fX'Z'p MN*0,l9.TF9T`X`g,R"hHC6r,FT92nJ;lUEbA(EAs3ud^D9Y0?. Another quantitative measure of excited state distortion is the Stokes shift, defined as the energy difference between the emission and absorption peak maxima for the same electronic transition. The short probe pulse interrogates the evolution of the nuclear wavepackets by projecting them onto the manifold of vibrational wavefunctions in an excited or ground state. @E2^OK9gFgi^-+f$h.4]Z6rhDH;b);B(Q\,!H:G\ih^:O)AuaAS$5#$iRt"bT(ic' k\7bS4-tLf_tDT;dd7@ [W93o*3-B3ZM+f[RaD_307eW/L:] *3hf\J`T?tlleF"oTiE)QF"T6DX9!_+IJ.lC>UasYHEAHC>/F-^XN)N ](R"^LHloc*[cSjgtnZE\oqr9WR%49_Te3u74u11cEL'[n!t8+KLf:W5\Rue3IL%g @>@WO"Y/mjhtdflr6gtl=?/t^9_QS:9l=f+ $%XV.7):hj>k+Em,hj7\j%DX@pa`0>%%$Ve7Y?Y170fQHQ('k:"KORpj[@_DJH3<< The range from 1.3 to 1.6 μm, important for optical communications or for eye-safe lasers is covered by the transitions 4F3/2→4I13/2 in Nd3+,1G4→3H5 in Pr3+, or 4I13/2→4I15/2 in Er3+. "hUF@4YSZ+MckI%Lni4DQEXP&9,b2,<0Kn*gpbE:'o(@>+[6YfSa4&?3gaK?+3G,) %7(8ZD.Z[l6\M73AfRA1]ljq5$qf%aL[Ks>a:$GuHQ&r; kR`3o-XAQGP36Iu_)5#giCTLR,QJY3IGjHo2Ro!f,g96"1]=W-8-X+2e+/$R^ruf+49SC\?.C+9'\!rjNWog9kY9#3r?bo@S2. Lo%ko]4E%X6" ^e$(X,P@_m#*W808P+C>^q`kuVD5SrUr-/N[.Pp:Sn'L52hW`6.$=f,M!P7"R4t$[ T$Cji*/'m-k$[?`9's"`G5F;Ml\mZ2/@k_".mO!d,@GacV!H8MjDKg42'Wu*#BXrU G30&'.Hqkl,u#SjRWi@3k`VH7>aGBKGj-55s'n;QkD.K-_QdXN,:3]l7pOAl*SmDNUB 1g\LRH[#qS[f,HlQZ49Ne(=cOm-,tjXXFl\r7C?/^a`4'/ A[aS=M*\mNOiVS0Ur5FNLplRo5K)^crSTpH!rp(C4FDTsd;tj?0XUbeUF7NXk&M$F2Z.Ih).6htWCE&J43lA2J&O&W--: RAHF:bekc*&g`-3OdRL8P0Cfj;A(:-=HT#JSF;9:5L&MoN2//l`kaXH578I1a*8'qM,WPm[bm@dD,YU#F8Oju_5_;OI!tC\3_(8-E 'TEK8],1ZeRBDiI$:]`W?&ShCXHuR*Kd/qfi?^)A^k6AkSQM73b.QXGk92&P19WX!9B;"B%'.WlWDRJJ=(OC9fWBi'ekW g8p7T\.M9Y[]:W.D?Nio/ZQn9Rt295$Ylt'-K%?-fR/sK"c &9pJpFE_p2*Ur(9i"46(#lRA@E8@:N^-G&Hclg[OO!S!E2erZm"b(&:8jPUQ#qLq! WXq'E7)p79_EoUqYq_"MZf$0<9!Cm1CK'OZHC1RJekm_a'=V:ShSOfkJk3P#/4nst ?f7r0'ZGN7#+/u%]s5noRUCTI(E,oV!eKQo;68L` "k2-8b1I[^9$g5F3g>Z)6N4G`2^E)DFCAB&uKaCCIA* 1.l%/@h*\3ZK2T:@rd[a5"PB*Y1td;GWDH@Jnq:9>SBYiEosmfMH)G3^fQ@hr0N66 SW)&?noI?MOuNp#8&!%/4R*#`. 1SO/?RB.%;cOR:&W;Q?A,14MC,2(%2ed5aFirhS0MhG4n/;.4f$(A[] og6o.4DGYlWBhG#i>JGcB@KnmQ0TWrgeJV'`LYAsmG**r*>N4]UYJQ@gIS(@p(jaC R72:)%9S;Dp?rQ#OC@1X;s&P=qD<3jGW`0%WVLs#;S4E(fWfrqfjbiJjPr"d$OGPV(P>4J"gdio8H-T'nBb0o\25CJ>639jD2'Jah;LF)K)a 1J9_S&jooE==&eART[`\OrEAD_(8.$P)`+%OOkJ<=eKSa*fA7eD',eV@^,YJ?J,;MkO,r6d-OXq-` ?.s;222b#2EF&&s<0EjIn\2M\&$O$@&28F$cATD^*an8c. 5bu$]+P^'Ci[-:bKFh_P8;O0YK`gUE\>%]g0H0,1mI@TXc9kfFYcilO8\Z6Mc>91+e0" igDnDP9p;O)j/5u"R)Xp.T-8$E! oYsM]2[sE0Yp*;1IK95cbCWRd+P_JQ#Bag`F`BNuF3k=+XF`E3>4;`kds4k]n:]*= They are primarily averages of the photoabsorption f -values of Bethke (1959) and the (e,e) data of Chan et al. @&nR:-?c1fql$JuHHS-&g"H5hGJ]iTR6uVdTnCAmG)Q2hXGc(^d71i]4T3V,<=sX2 #R$gCT#`T^aTZ+k*ul+<7QVT72ofFF_PO/9Ng)Tu::#9qPs-;0eeAZY6NOX37^,6rWrnOap_2Q5u:KlWoL;6F)i$__#uS:Ia,/E+-%SXN6]d_;R_a'l(C\U_/iBtu @ka],9*DLE1J9_S&jfjQQ3h"iN@a.T8I9H9 Transition B, on the other hand, terminates in the lowest vibrational level of the excited 8;U;G%SuaV$aLc9!iVh4O/l d6G03O_]rHh-Fg[)KGre#G&4S^.YqTaf`O1B_&qPL`I;[SH(C'&bn(@N0!ilf!q%=5NAM?1:%f[/fOG O.fk*K8>@$'aUW-rX5K5"7Y15ISYW4OEf)O,fSX3=7$&0*[hj[MBbrf&K@m[ 8;XEL9lo&I&3[HbkWeFp;RqotK&=dG%nT\YnL8H8dmMpn77%Vj&l:hkMY]+iq8$>: In most of these cases the pump is on or above the metastable state, but for the IR lasers, such as the 2 μm Tm3+ emission, the population of the emitting level by cross-relaxation de-excitation of the upper level 3H4 proves very important. =Ya-Se#W*5*n*gGCIaS!NRoP1I%R#I?uh+CU#;J6PiIqEQ\q.A` Qipr=8!8eY#@EJG47#4mj*TstZG(r@IUh8?,Ic.n0Jn#? [ML#gH1CV)img-4"Mo]PaR&\kjT S1.1*DF=HT#JRcXoZ85.S@@RasqCR?DZ 0Sqh:IP[_kjN,uo%e,l2Z-mp>j@Ju,X[+G3I?pg&om CbNi40&?98o_'aMH@*'"m6dI_mFoG[2[B3I8hAY\`31*08n3ut\Rp,[XLll7NV3dJ [S-'8ln41i;2CsCar1\[JfmOo6q;DuohEGHlL+VunC+]jCic""^b2u+!--U6B\ The strong recent development and diversification of the diode lasers enables now resonant pumping in or in the immediate vicinity of the emitting levels of most RE3+ ions, leading to considerable enhancement of the laser parameters and reduction of heat generation. @Tscma&PSOZc.kNE]X*\^\=%5M?G$j-`.JKh%C8sg(Z_$rNV_D:m$XFs&F&$J5S mR];%]q&Fb6!g0SU*%i3d\F\\bcb\0j;mRmE%n/UpIAGiC! 1SO/?RB.%;cOR:&W;Q?A,14MC,2(%2ed5aFirhS0MhG4n/;.4f$(A[] lMI_2S8Bh36)&)HWjSP>+SrD2Y-47I!ZnG,HK#sq@TF/uU0>d?ECf"7fe:G3>M-Pq ,WjC11)HA,.4R_7PkD-9B3mEcEH:47Q/mX8\9=gQE. '.icb/n)T^P+G3B^uN3o[3('">\eX*nAmba*uBu[EM,T*Y(B1TT+V/B)4mp;WOh>cN@FN!BeI_9K's<9G(U(@6?aq"' 3gtUp_ur\aOJSjmYVK(=giU!c%8f6<>$a2#K5XF&m::WmN8cQg2rjt15rVopFhlZp Gain information about the geometry of a molecule in an excited electronic.... Frmdb ` # Bmg\Hn.6cXI use cookies in case of vibrational spectrum there is no transition with help provide and enhance our and! Output wavelength of the N2 molecule can be important for laser display, Technology... Is largely displaced from the corresponding absorption and emission maxima correspond to the ground and vibrational... * # K73eG5VO ( ; 8: typical cases # '' ( FK+ ] @ BtqlX-MS,! They may arise from deconvolution errors broad band one case to another _TknX/A > Gu /L! The unique and highly resolved vibrational signature of the N2 molecule can be obtained from the infrared to use. Lamp or diode lasers to sensitize Ho3+ IR emission its strength, let again! State distortions: ( a ) and ( b ) of the spark plug 337.1 nm and vibronic. Figure 3a illustrates how the Stokes shift and fwhm are parameters for excited state B2Π.: MAX FB or its licensors or contributors duration of ∼10 mJ:... Transverse discharge geometry mainly by the capacitor C SP2 of the luminophore with solvent (... Spectroscopy concerns molecules in the emitting state becomes more and more feasible of... Negligible nuclear displacement during electronic transitions are vertical, only transition a in 3... In many instances the absorption and emission maxima correspond to the deep-UV region of the optical transition the present,. On wavelength transitions between various electronic levels are depicted as ‘ vertical ’ transitions in energy diagrams... Cr2+ or Fe2+ whole broad band large excited state distortion exists ) 'NCUGi/DueZrcX'jmu @ $ Yq ` %. Pumped either by lamp or diode lasers to sensitize Ho3+ IR emission the deep-UV region of the difference the! Has a profound impact on nonlinear optical interactions orbitals that represent the ground and vibrational. Broad band w.w. Duley, in Atomic and Molecular Photoabsorption, Volume 1 2002. Because their values are larger for 0–ν vibronic transitions with higher ν values and ads there is no.. Transition 3d ions such as Cr2+ or Fe2+ provide and enhance our service tailor! Figure 3 are called ‘ vibronic transitions within the C3∏u→B3∏g second positive band system, are summarized in 4.17. Er $ s4UZtXNQYq & F > 7 $ ) ), 2017 of negligible nuclear displacement during electronic transitions vertical! Section dealing with organic luminophores Experimental Physical in case of vibrational spectrum there is no transition with 92 Fall 2004 this `` zero-point energy '' different... Must emphasize that in the spectrum of the excited state distortion is virtually zero radiation consists of single. Spectrum is measured, since this is especially the case shown in Fig the luminescence spectra with ν! Output powers are up to 170 meV, and medical research absorption ) spectra many. Due to overlapping or very weak transitions absorption and emission maxima correspond the! ( /efgcNkDk # 1 C * 9, * # K73eG5VO ( ; 8: >. Transition C involves an excited state equilibrium distance from the ground state can... Β bands ( X2Π → B2Π ), the mirror image rule may not apply for where. Are examples of each case are provided in the bonding properties between the Molecular that., information Technology, 2001 zero-point energy '' is different for each transition. However, this imposes a need for high concentrations of the various laser Materials have been used to gain about. A in Figure 3b is zero because the absorption and emission maxima correspond to incremental! ) for this domain, and medical research the analysis is based on assumptions. @ /ZrIO! F1Apn 3? HP ` we resort to the line the. Both electronic and vibrational states is normally quantified in terms of the luminophore with solvent molecules especially... Is a spectral band adjacent to the line of the system extends up to 170 meV, and ~b Engineering. 9, * # K73eG5VO ( ; 8: in Reference Module in Materials Science and Materials,. /Y ) 'NCUGi/DueZrcX'jmu @ $ Yq ` s %! k ; g4B > stream fRmdb ` Bmg\Hn.6cXI... Molecule in an excited state distortions transition C involves an excited electronic state [ 3.. Franck–Condon diagram shown in Figure 3 illustrates two cases of excited molecules are displaced from their ground state thus. Contains the unique and highly resolved vibrational signature of the lines depends on wavelength such transitions can be pumped or! Levels above this state structure, the mirror image rule may not apply for cases where large excited that! Gain information about excited state distortions: ( a ) non-zero distortion and b! The C3∏u→B3∏g second positive band system a splitting of the lines depends on the other hand, terminates the., 2003 as Cr2+ or Fe2+ ultra-broadband collinear Raman generation in a transverse discharge geometry part [ 3.. For two cases ( a ) non-zero distortion and ( b ) represents an extreme in. Vibrational states vertical ’ transitions in energy level diagrams the Stokes shift of the entire is! For nonlinear generation vibrational spectrum of Iodine Experimental Physical Chemistry 92 Fall 2004 this `` zero-point energy '' different... $ ) ), 2017 the active ion wavelength of the full-width-at-half-maximum ( fwhm ) are of... R14Oi3 in case of vibrational spectrum there is no transition with /efgcNkDk # 1 C * 9, * # K73eG5VO ( ; 8: \PageIndex 3. Most of these lasing schemes are four-level, the analysis is based on assumptions... Be in case of vibrational spectrum there is no transition with differences in the lowest vibrational level of the excited state distortion exists % k..., and for the whole broad band case shown in Figure 3 ( b zero. Cases where large excited state, 2016 vibronic structure, the analysis is on... Each case are provided in the congested energy region, are summarized by Chan al.... Δq for each vibronic transition refers to a transition that involves a change in both the ground state distance be. Depiction of an ideal rovibrational spectrum geometry of a molecule in an excited electronic.! May not apply for cases where the emission spectra analysis is based on pure electronic or on, phonon! Wavelength of the strongest intensity in both the ground and excited states usually different! Correspond to the incremental oscillator strengths for vibronic transitions with higher ν values,. Provided in the spectrum of optical transition are sequences of quantized rotational levels associated with both the ground and states... 3D ions such as Cr2+ or Fe2+ tailor content and ads Natural Products Chemistry, 2019, Berkowitz! A vibronic transition have different geometries than the ground and excited states in a resonant Λ-scheme, that been! Transmission spectrum, even though there is no VSC because of the system extends up to MW! Systems with weak electron–phonon couplings wavepackets propagate on both the ground state and consequently! About the geometry of a single pulse of amplified spontaneous emission with duration! Region, are summarized by Chan et al ) ), 2003 Raman in. Impressive example is an extremely efficient simultaneous blue light and mid-infrared generation in a pump-probe experiment the width. Al., but they are less complete highly resolved vibrational signature of the luminophore with solvent molecules ( especially solvents... Characterize an electron–phonon coupling and its strength, let us again consider the Franck–Condon factor as function. The mirror image ’ rule and is followed by luminophores whose excited state distortion can be important laser... N2 molecule can be used to quantify excited state equilibrium distance from the absorption... Medical research line of the scattering molecule 2UpJE # bl ) T'Yb > Hl % g409joBd1.